US6864392B2 - α-Sulfin and α-Sulfonamino amide derivatives - Google Patents

α-Sulfin and α-Sulfonamino amide derivatives Download PDF

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US6864392B2
US6864392B2 US10/257,085 US25708503A US6864392B2 US 6864392 B2 US6864392 B2 US 6864392B2 US 25708503 A US25708503 A US 25708503A US 6864392 B2 US6864392 B2 US 6864392B2
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alkyl
compound
optionally substituted
hydrogen
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Martin Zeller
Clemens Lamberth
Henry Szczepanski
Alain De Mesmaeker
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Syngenta Crop Protection LLC
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    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N41/00Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a sulfur atom bound to a hetero atom
    • A01N41/02Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a sulfur atom bound to a hetero atom containing a sulfur-to-oxygen double bond
    • A01N41/04Sulfonic acids; Derivatives thereof
    • A01N41/06Sulfonic acid amides
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C307/00Amides of sulfuric acids, i.e. compounds having singly-bound oxygen atoms of sulfate groups replaced by nitrogen atoms, not being part of nitro or nitroso groups
    • C07C307/04Diamides of sulfuric acids
    • C07C307/06Diamides of sulfuric acids having nitrogen atoms of the sulfamide groups bound to acyclic carbon atoms
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C311/00Amides of sulfonic acids, i.e. compounds having singly-bound oxygen atoms of sulfo groups replaced by nitrogen atoms, not being part of nitro or nitroso groups
    • C07C311/01Sulfonamides having sulfur atoms of sulfonamide groups bound to acyclic carbon atoms
    • C07C311/02Sulfonamides having sulfur atoms of sulfonamide groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
    • C07C311/03Sulfonamides having sulfur atoms of sulfonamide groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton having the nitrogen atoms of the sulfonamide groups bound to hydrogen atoms or to acyclic carbon atoms
    • C07C311/06Sulfonamides having sulfur atoms of sulfonamide groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton having the nitrogen atoms of the sulfonamide groups bound to hydrogen atoms or to acyclic carbon atoms to acyclic carbon atoms of hydrocarbon radicals substituted by carboxyl groups
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C313/00Sulfinic acids; Sulfenic acids; Halides, esters or anhydrides thereof; Amides of sulfinic or sulfenic acids, i.e. compounds having singly-bound oxygen atoms of sulfinic or sulfenic groups replaced by nitrogen atoms, not being part of nitro or nitroso groups
    • C07C313/02Sulfinic acids; Derivatives thereof
    • C07C313/06Sulfinamides

Definitions

  • the present invention relates to novel ⁇ -sulfin and ⁇ -sulfonamino acid amides of formula I below. It relates to the preparation of those substances and to agrochemical compositions comprising at least one of those compounds as active ingredient. The invention relates also to the preparation of the said compositions and to the use of the compounds or of the compositions in controlling or preventing the infestation of plants by phytopathogenic microorganisms, especially fungi.
  • the invention relates to ⁇ -sulfin- and ⁇ -sulfonamino acid amides of the general formula I including the optical isomers thereof and mixtures of such isomers, wherein
  • aryl includes aromatic hydrocarbon rings like phenyl, naphthyl, anthracenyl, phenanthrenyl, with phenyl being preferred.
  • Heteroaryl stands for aromatic ring systems comprising mono-, bi- or tricyclic systems wherein at least one oxygen, nitrogen or sulfur atom is present as a ring member.
  • Examples are furyl, thienyl, pyrrolyl, imidazolyl, pyrazolyl, thiazolyl, isothiazolyl, oxazolyl, isoxazolyl, oxadiazolyl, thiadiazolyl, triazolyl, tetrazolyl, pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, triazinyl, tetrazinyl, indolyl, benzothiophenyl, benzofuranyl, benzimidazolyl, indazolyl, benzotriazolyl, benzothiazolyl, benzoxazolyl, quinolinyl, isoquinolinyl, phthalazinyl, quinoxalin
  • aryl and heteroaryl groups may carry one or more identical or different substituents. Normally not more than three substituents are present at the same time.
  • substituents of aryl or heteroaryl groups are: alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkyl-alkyl, phenyl and phenyl-alkyl, it being possible in turn for all of the preceding groups to carry one or more identical or different halogen atoms; alkoxy; alkenyloxy; alkynyloxy; alkoxyalkyl; halogenalkoxy, alkylthio; halogenalkylthio; alkyl sulfonyl; formyl; alkanoyl; hydroxy; halogen; cyano; nitro; amino; alkylamino; dialkyl amino; carboxy; alkoxycarbonyl; alkenyloxycarbonyl; alkynyloxycarbonyl.
  • halogen or the prefix “halo” includes fluorine, chlorine, bromine and iodine.
  • alkyl, alkenyl and alkynyl radicals may be straight-chain or branched. This applies also to the alkyl, alkenyl or alkynyl parts of other alkyl-, alkenyl- or alkynyl-containing groups.
  • alkyl on its own or as part of another substituent is to be understood as being, for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl and the isomers thereof, for example isopropyl, isobutyl, tert-butyl or sec-butyl, isopentyl or tert-pentyl.
  • Cycloalkyl is, depending upon the number of carbon atoms mentioned, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl.
  • alkenyl as a group or as a structural element of other groups is to be understood as being, for example, ethenyl, allyl, 1-propenyl, buten-2-yl, buten-3-yl, penten-1-yl, penten-3-yl, hexen-1-yl, 4-methyl-3-pentenyl or 4-methyl-3-hexenyl.
  • Alkynyl as a group or as a structural element of other groups is, for example, ethynyl, propyn-1-yl, propyn-2-yl, butyn-1-yl, butyn-2-yl, 1-methyl-2-butynyl, hexyn-1-yl, 1-ethyl-2-butynyl or octyn-1-yl.
  • a halogenalkyl group may contain one or more (identical or different) halogen atoms, and for example may stand for CHCl 2 , CH 2 F, CCl 3 , CH 2 Cl, CHF 2 , CF 3 , CH 2 CH 2 Br, C 2 Cl 5 , CH 2 Br, CHClBr, CF 3 CH 2 , etc.
  • R 2 and R 3 together with the carbon atom to which they are attached form a hydrocarbon ring the ring corresponds to cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane or cyclooctane.
  • R 9 and R 10 together with the nitrogen atom to which they are attached form a ring system the ring corresponds to pyrrolidine or piperidine.
  • the presence of at least one asymmetric carbon atom and/or at least one asymmetric oxidized sulfur atom in the compounds of formula I means that the compounds may occur in optically isomeric forms. As a result of the presence of a possible aliphatic C ⁇ C double bond, geometric isomerism may also occur.
  • Formula I is intended to include all those possible isomeric forms and mixtures thereof.
  • Preferred individual compounds are:
  • ⁇ -sulfin- and ⁇ -sulfonamino acid derivatives having a different kind of molecular structure have already been proposed for controlling plant-destructive fungi (for example in WO 95/030651, WO 97/14677, WO 98/38160, WO 98/38161 and WO 99/07674).
  • ⁇ -sulfin- and ⁇ -sulfonamino acid amides of formula I may be obtained according to one of the following processes: a)
  • Carboxy-activated derivatives of the amino acid of formula II encompasses all compounds having an activated carboxyl group like an acid halide, such as an acid chloride, like symmetrical or mixed anhydrides, such as mixed anhydrides with O-alkylcarbonates, like activated esters, such as p-nitrophenylesters or N-hydroxysuccinimidesters, as well as in situ produced activated forms of the amino acid of formula II by condensating agents, such as dicyclohexylcarbodiimide, carbonyldiimidazol, benzotriazol-1-yloxy-tris (dimethylamino)phosphonium hexafluorophosphate, O-benzotriazol-1-yl N,N,N′,N′-bis(penta methylene)uronium hexafluorophosphate, O-benzotriazol-1-yl N,N,N′,N′-bis(tetramethylene)uronium hex
  • the mixed anhydrides of the amino acids of the formula II may be prepared by reaction of an amino acid of formula II with chloroformic acid esters like chloroformic acid alkylesters, such as ethyl chloroformate or isobutyl chloroformate, optionally in the presence of an organic or inorganic base like a tertiary amine, such as triethylamine, N,N-diisopropyl-ethylamine, pyridine, N-methyl-piperidine or N-methyl-morpholine.
  • chloroformic acid esters like chloroformic acid alkylesters, such as ethyl chloroformate or isobutyl chloroformate
  • an organic or inorganic base like a tertiary amine, such as triethylamine, N,N-diisopropyl-ethylamine, pyridine, N-methyl-piperidine or N-methyl-morpholine.
  • the present reaction is preferably performed in an inert solvent like aromatic, non-aromatic or halogenated hydrocarbons, such as chlorohydrocarbons e.g. dichloromethane or toluene; ketones, e.g. acetone; esters, e.g. ethyl acetate; amides, e.g. N,N-dimethylformamide; nitriles e.g. acetonitrile; or ethers e.g. diethylether, tert-butyl-methylether, dioxane or tetrahydrofurane or water. It is also possible to use mixtures of these solvents.
  • aromatic, non-aromatic or halogenated hydrocarbons such as chlorohydrocarbons e.g. dichloromethane or toluene; ketones, e.g. acetone; esters, e.g. ethyl acetate; amides, e
  • the reaction is preformed optionally in the presence of an organic or inorganic base like a tertiary amine, e.g. triethylamine, N,N-diisopropyl-ethylamine, pyridine, N-methyl-piperidine or N-methyl-morpholine, like a metal hydroxide or a metal carbonate, preferentially an alkali hydroxide or an alkali carbonate, such as lithium hydroxide, sodium hydroxide or potassium hydroxide at temperatures ranging from ⁇ 80° C. to +150° C., preferentially at temperatures ranging from ⁇ 40° C. to +40° C.
  • an organic or inorganic base like a tertiary amine, e.g. triethylamine, N,N-diisopropyl-ethylamine, pyridine, N-methyl-piperidine or N-methyl-morpholine, like a metal hydroxide or a metal carbonate, preferentially an al
  • the compounds of formula II may be prepared by reaction of an amino acid of formula IV where R 2 and R 3 are as defined for formula I with a sulfonyl halide or a sulfinyl halide of formula V where R 1 and n have the same meanings as defined above and where X is halide, preferentially chlorine or bromine (step A).
  • the reaction may be performed in an inert solvent like aromatic, non-aromatic or halogenated hydrocarbons, such as chlorohydrocarbons, e.g. dichloromethane or toluene; ketones, e.g. acetone; esters, e.g. ethyl acetate; ethers, e.g. diethylether, tert-butyl-methylether, dioxane or tetrahydrofurane or water. It is also possible to use mixtures of these solvents.
  • aromatic, non-aromatic or halogenated hydrocarbons such as chlorohydrocarbons, e.g. dichloromethane or toluene; ketones, e.g. acetone; esters, e.g. ethyl acetate; ethers, e.g. diethylether, tert-butyl-methylether, dioxane or tetrahydrofurane or
  • the reaction is performed optionally in the presence of an organic or inorganic base like a tertiary amine, such as triethylamine, N,N-diisopropyl-ethylamine, pyridine, N-methyl-piperidine or N-methyl-morpholine, like a metal hydroxide or a metal carbonate, preferentially an alkali hydroxide or an alkali carbonate, such as lithium hydroxide, sodium hydroxide or potassium hydroxide at temperatures ranging from ⁇ 80° C. to +150° C., preferentially at temperatures ranging from ⁇ 40° C. to +40° C. b)
  • a tertiary amine such as triethylamine, N,N-diisopropyl-ethylamine, pyridine, N-methyl-piperidine or N-methyl-morpholine
  • an organic or inorganic base like a tertiary amine, such as triethylamine, N,N-
  • the compounds of formula I may also be prepared by reaction of an amino acid derivative of formula VI wherein R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 are as defined for formula I with a sulfonyl halide or a sulfinyl halide of formula V wherein R 1 and n are as defined for formula I and X is halide, preferentially chlorine or bromine (step C).
  • step C preferentially chlorine or bromine
  • the compounds of formula I may also be prepared by reaction of a phenol of formula VII wherein R 1 , n, R 2 , R 3 , R 4 , R 5 , R 6 and R 7 are as defined for formula I with a compound of formula VIII wherein R 8 is as defined for formula I and Y is a leaving group like a halide such as a chloride or bromide or a sulfonic ester such as a tosylate, mesylate or triflate (step D).
  • the reaction may be performed in an inert solvent like aromatic, non-aromatic or halogenated hydrocarbons, such as chlorohydrocarbons e.g. dichloromethane or toluene; ketones e.g.
  • esters e.g. ethyl acetate; ethers, e.g. diethylether, tert-butyl-methylether, dioxane or tetrahydrofurane, amides, e.g. dimethylformamide, nitriles, e.g. acetonitrile, alcohols, e.g. methanol, ethanol, isopropanol, n-butanol or tert-butanol, sulfoxides e.g. dimethylsulfoxide or water. It is also possible to use mixtures of these solvents.
  • the reaction is performed optionally in the presence of an organic or inorganic base like a tertiary amine, such as triethylamine, N,N-diisopropyl-ethylamine, pyridine, N-methyl-piperidine or N-methyl-morpholine, like a metal hydroxide, a metal carbonate or a metal alkoxide, preferentially an alkali hydroxide, an alkali carbonate or an alkali alkoxide, such as lithium hydroxide, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium methoxide, potassium methoxide, sodium ethoxide, potassium ethoxide, sodium tert-butoxide or potassium tert-butoxide at temperatures ranging from ⁇ 80° C. to +200° C., preferentially at temperatures ranging from 0° C. to +120° C. d)
  • an organic or inorganic base like a tertiary amine, such as
  • the compounds of formula Ia may also be prepared via formula IX wherein R 1 , n, R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 11 , R 12 and R 13 are defined for formula I by reacting of a phenol of formula VII wherein R 1 , n, R 2 , R 3 , R 4 , R 5 , R 6 and R 7 are as defined for formula I with a compound of formula VIIIa wherein R 11 , R 12 and R 13 are as defined for formula I and Y is a leaving group like a halide such as a chloride or bromide or a sulfonic ester such as a tosylate, mesylate or triflate (step E).
  • a halide such as a chloride or bromide
  • a sulfonic ester such as a tosylate, mesylate or triflate
  • reaction is performed in the same manner as described for step D.
  • the compounds of formula Ia R 11 , R 12 and R 13 is as defined for formula I may be prepared by reaction of compounds of formula IX with hydrogen.
  • the reaction is performed in a solvent like ethers, e.g. diethylether, dioxane or tetrahydrofuran, or like alcohols, e.g. methanol or ethanol, or water in the presence of transition metals or transition metal salts, e.g. nickel, cobalt, palladium, platinum or rhodium, optionally in the presence of bases, e.g. ammonia, or in the presence of salts, e.g. barium sulfate, at temperatures ranging from ⁇ 20° C. to +160° C. and at pressures ranging from 1 to 200 bar.
  • the intermediate amines of formula III may be obtained by one of the following processes:
  • Step 1 is the alkylation of a phenol with a compound of formula VIII.
  • the reaction is performed in the same manner as described for procedure c).
  • Step 2 is the reaction of an aromatic aldehyde with nitromethane. This reaction is performed in a solvent like an organic carboxylic acids, e.g. acetic acid optionally in the presence of the ammonium salt of this carboxylic acid, e.g. ammonium acetate at temperatures ranging from 0° C. to +200° C.
  • a solvent like an organic carboxylic acids e.g. acetic acid optionally in the presence of the ammonium salt of this carboxylic acid, e.g. ammonium acetate at temperatures ranging from 0° C. to +200° C.
  • Step 3 is the reduction of an unsaturated nitrogen-compound.
  • This reaction is performed in a solvent like an ether, e.g. diethylether, dioxane or tetrahydrofuran, or an alcohol, e.g. methanol, ethanol or isopropanol, with borohydride, with a boron-complex, e.g. the complex of borohydride with tetrahyrofuran, with an alkaliborohydride, with an alkalialuminiumhydride, e.g.
  • a transition metal e.g. nickel, cobalt, palladium, platinium or rhodium at temperatures ranging from ⁇ 50° C. to +200° C.
  • Step 4 is the reaction of an aldehyde or a ketone of formula XXIII with hydroxylamine or with a salt of hydroxylamine.
  • This reaction is performed in a solvent like an alcohol, e.g. methanol, ethanol or isopropanol, like an ether, e.g. diethylether, dioxane or tetrahydrofuran, like an amide, e.g. dimethylformamide, or in water or in a mixture of these solvents optionally in the presence of an organic or inorganic base like a tertiary amine, e.g. triethylamine, like a heterocyclic compound containing nitrogen, e.g. pyridine, or like an alkalicarbonate, e.g. sodium carbonate or potassium carbonate, at temperatures ranging from ⁇ 20° C. to +150° C.
  • an alcohol e.g. methanol, ethanol or isopropanol
  • an ether
  • Step 5 is the exchange of hydroxy by cyanide.
  • This reaction is performed in an organic solvent like an amide, e.g. dimethylformamide using a metal cyanide like an alkali cyanide, e.g. sodium cyanide or potassium cyanide, at temperatures ranging from 0° C. to +200° C.
  • a metal cyanide like an alkali cyanide, e.g. sodium cyanide or potassium cyanide
  • Step 6 is the hydrolysis of an alkyl ester.
  • This reaction is performed in a solvent like an alcohol, e.g. methanol, ethanol or isopropanol, like an ether, e.g. diethylether, dioxane or tetrahydrofuran, like a halogenated hydrocarbon, e.g. dichloromethane, or water or in a mixture of these solvents optionally in the presence of an alkali hydroxide, e.g. lithium hydroxide, sodium hydroxide or potassium hydroxide, or optionally in the presence of an acid, e.g. hydrogen chloride, sulfuric acid or trifluoroacetic acid at temperatures ranging from ⁇ 20° C. to +160° C.
  • an alcohol e.g. methanol, ethanol or isopropanol
  • an ether e.g. diethylether, dioxane or tetrahydrofuran
  • a halogenated hydrocarbon
  • Step 7 is the reaction of a carboxylic acid or the activated form of this carboxylic acid with hydrogen azide or an azide-salt.
  • An activated form of a carboxylic acid can be the acid halogenide, e.g. acid chloride, a symmetric or a mixed anhydride.
  • Azide-salts can be alkali azides, e.g. sodium azide.
  • the reaction is performed in a solvent like a hydrocarbon, e.g. toluene or xylene, like a halogenated hydrocarbon, e.g. chloroform, like an ether, e.g. dioxane, like a ketone, e.g.
  • acetone or 2-butanone like an alcohol, e.g. methanol, ethanol or tert-butanol, or water or in a mixture of these solvents optionally in the presence of an acid like an inorganic acid, e.g. sulfuric acid or hydrogen chloride at temperatures ranging from ⁇ 40° C. to +200° C.
  • an acid like an inorganic acid, e.g. sulfuric acid or hydrogen chloride at temperatures ranging from ⁇ 40° C. to +200° C.
  • the compounds of formula XXVI are prepared starting from compounds of the formula XXV by applying step 5 and step 1 in the same pot.
  • Amines of formula VI can be obtained by the following process: wherein R is lower alkyl or optionally substituted benzyl.
  • Step 8 is the amidation of an carbamate-protected amino acid of formula XXXIII with an amine of formula XXXIV.
  • the reaction is performed in the same manner as described for step A.
  • Step 9 is the alkylation of a phenol of formula XXXV with an compound of formula VIII.
  • the reaction is performed in the same manner as described for step D.
  • Step 10 is the hydrolysis of a carbamate of formula XXXVI.
  • the reaction is performed in a solvent like hydrocarbons, e.g. toluene, like halogenated hydrocarbons, e.g. dichloromethane, like ketones, e.g. acetone, like esters, e.g. ethyl acetate, like ethers, e.g. dioxane or tetrahydrofuran, or like water or in mixtures of these solvents optionally in the presence of an organic acid like carboxylic acid, e.g. trifluoroacetic acid, or like a sulfonic acid, e.g. methanesulfonic acid or toluenesulfonic acid, or in the presence of an inorganic acid, e.g. hydrogen chloride or sulfuric acid, at temperatures ranging from ⁇ 40° C. to +160° C.
  • an organic acid e.g. hydrogen chloride or sulfuric
  • the compounds of formula I are oils or solids at room temperature and are distinguished by valuable microbiocidal properties. They can be used in the agricultural sector or related technical fields preventively and curatively for the control of plant-destructive microorganisms.
  • the compounds of formula I according to the invention are distinguished at low rates of concentration not only by outstanding microbiocidal, especially fungicida I, activity but also by being especially well tolerated by the treated crop plants.
  • the compounds of formula I have a very advantageous biocidal spectrum in the control of phytopathogenic microorganisms, especially fungi.
  • the compounds of formula I it is possible to inhibit or destroy phytopathogenic microorganisms that occur on various crops of useful plants or on parts of such plants (fruit, blossom, leaves, stems, tubers, roots), while parts of the plants which grow later also remain protected, for example, against phyto pathogenic fungi.
  • novel compounds of formula I prove to be effective against specific genera of the fungus classes Fungi imperfecti (e.g. Cercospora ), Basidio mycetes (e.g. Puccinia ) and Ascomycetes (e.g. Erysiphe and Venturia ) and especially against Oomycetes (e.g. Plasmopara, Peronospora, Pythium and Phytophthora ). They therefore represent in plant protection a valuable addition to the compositions for controlling phyto pathogenic fungi.
  • the compounds of formula I can also be used as coatings or dressings for protecting seed (fruit, tubers, grains) and plant cuttings from fungal infections and against phyto pathogenic fungi that occur in the soil.
  • the invention relates also to compositions comprising compounds of formula I as active ingredient, especially plant-protecting compositions, and to the use thereof in the agricultural sector or related fields.
  • the present invention includes the preparation of those compositions, wherein the active ingredient is homogeneously mixed with one or more of the substances or groups of substances described herein. Also included is a method of treating plants which is distinguished by the application of the novel compounds of formula I or of the novel compositions.
  • Target crops to be protected within the scope of this invention comprise, for example, the following species of plants: cereals (wheat, barley, rye, oats, rice, maize, sorghum and related species); beet (sugar beet and fodder beet); pomes, stone fruit and soft fruit (apples, pears, plums, peaches, almonds, cherries, strawberries, raspberries and blackberries); leguminous plants (beans, lentils, peas, soybeans); oil plants (rape, mustard, poppy, olives, sunflowers, coconut, castor oil plants, cocoa beans, groundnuts); cucurbitaceae (marrows, cucumbers, melons); fibre plants (cotton, flax, hemp, jute); citrus fruit (oranges, lemons, grapefruit, mandarins); vegetables (spinach, lettuce, asparagus, cabbages, carrots, onions, tomatoes, potatoes, paprika); lauraceae (avocado, cinnamon, camphor) and plants such as
  • the compounds of formula I are normally used in the form of compositions and can be applied to the area or plant to be treated simultaneously or in succession with other active ingredients.
  • Those other active ingredients may be fertilisers, micronutrient donors or other preparations that influence plant growth. It is also possible to use selective herbicides or insecticides, fungicides, bactericides, nematicides, molluscicides or mixtures of several of those preparations, if desired together with further carriers, surfactants or other application-promoting adjuvants customarily employed in formulation technology.
  • the compounds of formula I can be mixed with other fungicides, resulting in some cases in unexpected synergistic activities.
  • azoles such as azoles, such as azaconazole, bitertanol, bromuconazole, cyproconazole, difenoconazole, diniconazole, epoxiconazole, fenbuconazole, fluquinconazole, flusilazole, flutriafol, hexaconazole, imazalil, imibenconazole, ipconazole, metconazole, myclobutanil, pefurazoate, penconazole, pyrifenox, prochloraz, propiconazole, tebuconazole, tetraconazole, triadimefon, triadimenol, triflumizole, triticonazole; pyrimidinyl carbinols, such as ancymidol, fenarimol, nuarimol; 2-amino-pyrimidines, such as bupirimate, di
  • Suitable carriers and surfactants may be solid or liquid and correspond to the substances ordinarily employed in formulation technology, such as e.g. natural or regenerated mineral substances, solvents, dispersants, wetting agents, tackifiers, thickeners, binders or fertilisers. Such carriers and additives are described, for example, in WO 95/30651.
  • a preferred method of applying a compound of formula I, or an agrochemical composition comprising at least one of those compounds, is application to the foliage (foliar application), the frequency and the rate of application depending upon the risk of infestation by the pathogen in question.
  • the compounds of formula I may also be applied to seed grains (coating) either by impregnating the grains with a liquid formulation of the active ingredient or by coating them with a solid formulation.
  • the compounds of formula I are used in unmodified form or, preferably, together with the adjuvants conventionally employed in formulation technology, and are for that purpose advantageously formulated in known manner e.g. into emulsifiable concentrates, coatable pastes, directly sprayable or dilutable solutions, dilute emulsions, wettable powders, soluble powders, dusts, granules, and by encapsulation in e.g. polymer substances.
  • the methods of application such as spraying, atomising, dusting, scattering, coating or pouring, are chosen in accordance with the intended objectives and the prevailing circumstances.
  • Advantageous rates of application are normally from 1 g to 2 kg of active ingredient (a.i.) per hectare (ha), preferably from 10 g to 1 kg a.i./ha, especially from 25 g to 750 g a.i./ha.
  • rates of from 0.001 g to 1.0 g of active ingredient per kg of seed are advantageously used.
  • compositions, preparations or mixtures comprising the compound(s) (active ingredient(s)) of formula I and, where appropriate, a solid or liquid adjuvant are prepared in known manner, e.g. by homogeneously mixing and/or grinding the active ingredient with extenders, e.g. solvents, solid carriers and, where appropriate, surface-active compounds (surfactants).
  • extenders e.g. solvents, solid carriers and, where appropriate, surface-active compounds (surfactants).
  • the agrochemical compositions usually comprise 0.01 to 99% by weight, preferably 0.1 to 95% by weight, of a compound of formula I, 99.99 to 1% by weight, preferably 99.9 to 5% by weight, of a solid or liquid adjuvant, and 0 to 25% by weight, preferably 0.1 to 25% by weight, of a surfactant.
  • compositions may also comprise further ingredients, such as stabilisers, antifoams, viscosity regulators, binders and tackifiers, as well as fertilisers or other active ingredients for obtaining special effects.
  • further ingredients such as stabilisers, antifoams, viscosity regulators, binders and tackifiers, as well as fertilisers or other active ingredients for obtaining special effects.
  • R 1 R 3 R 8 001 CH 3 — CH 3 —CH 2 — CH 3 —(CH 2 ) 3 —C ⁇ C—CH 2 — 002 CH 3 —CH 2 — CH 3 —CH 2 — CH 3 —(CH 2 ) 3 —C ⁇ C—CH 2 — 003 (CH 3 ) 2 N— CH 3 —CH 2 — CH 3 —(CH 2 ) 3 —C ⁇ C—CH 2 — 004 CH 3 —CH 2 —CH 2 — CH 3 —CH 2 — CH 3 —(CH 2 ) 3 —C ⁇ C—CH 2 — 005 (CH 3 ) 2 CH— CH 3 —CH 2 — CH 3 —(CH 2 ) 3 —C ⁇ C—CH 2 — 006 Cl—CH 2 —CH 2 —CH 2 — CH 3 —CH 2 — CH 3 —(CH 2 ) 3 —C ⁇ C—CH 2 — 007 CH 3
  • R 1 R 3 001 (CH 3 —CH 2 ) 2 N— CH 3 —CH 2 — 002 CH 3 —CH 2 —(CH 3 )N— CH 3 —CH 2 — 003 CH 3 —CH 2 — 004 CH 3 —(CH 2 ) 2 —CH 2 — CH 3 —CH 2 — 005 (CH 3 ) 2 CH—CH 2 — CH 3 —CH 2 — 006 CH 3 —CH 2 —(CH 3 )CH— CH 3 —CH 2 — 007 (CH 3 ) 3 C— CH 3 —CH 2 — 008 CH 2 ⁇ CH— CH 3 —CH 2 — 009 CH 3 —CH 2 — 010 (CH 3 —CH 2 ) 2 N— (CH 3 ) 2 CH— 011 CH 3 —CH 2 —(CH 3 )N— (CH 3 ) 2 CH— 012 (CH 3 ) 2 CH— 013 CH 3 —(
  • Formulations may be prepared analogously to those described in, for example, WO 95/30651.
  • Compounds of Tables 1 to 15 exhibit a good fungicidal action against Plasmopara viticola on vines.
  • Compounds A1.1, A1.2, A1.3, A1.4, A1.5 and A1.6 at 200 ppm inhibit fungal infestation in this test to a least 80%, while under the same conditions untreated control plants are infected by the phytopathogenic fungi to over 80%.

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Abstract

The invention relates to novel pesticidally active α-sulfin- and α-sulfonamino acid amides of the general formula (I) including the optical isomers thereof and mixtures of such isomers, wherein n is a number zero or one, R1-R7 have the meanings given in the specification. R8 is either hydrogen, (a), (b), (c), (d) or (e) wherein R11, R12, R14, R15 and R17 are each independently hydrogen or C1-C4alkyl, R13 is C4-C12alkyl; C1-C12 halogenalkyl; C3-C8 cycloalkyl; optionally substituted aryl or optionally substituted heteroaryl, R16 is optionally substituted aryl or optionally substituted heteroaryl; and Z is oxygen, sulfur —CR18R19— or —NR20—, wherein R18, R19, R20 independently of each other are hydrogen or C1-C4alkyl. The novel compounds possess plant-protecting properties and are suitable for protecting plants against infestation by phytopathogenic microorganisms
Figure US06864392-20050308-C00001

Description

This application is a 371 of PCT/EP01/04207, filed Apr. 11, 2001.
The present invention relates to novel α-sulfin and α-sulfonamino acid amides of formula I below. It relates to the preparation of those substances and to agrochemical compositions comprising at least one of those compounds as active ingredient. The invention relates also to the preparation of the said compositions and to the use of the compounds or of the compositions in controlling or preventing the infestation of plants by phytopathogenic microorganisms, especially fungi.
The invention relates to α-sulfin- and α-sulfonamino acid amides of the general formula I
Figure US06864392-20050308-C00002

including the optical isomers thereof and mixtures of such isomers,
wherein
    • n is a number zero or one;
    • R1 is C1-C12alkyl, C1-C12alkyl substituted with C1-C4alkoxy, C1-C4alkylthio, C1-C4alkylsulfonyl, C3-C8cycloalkyl, cyano, C1-C6alkoxycarbonyl, C3-C8alkenyloxycarbonyl or C3-C6alkynyloxycarbonyl; C3-C8cycloalkyl; C2-C12alkenyl; C2-C12alkynyl; C1-C12halogenalkyl; or a group NR9R10 wherein R9 and R10 are each independently of the other hydrogen or C1-C6alkyl, or together are tetra- or penta-methylene;
    • R2 and R3 are each independently hydrogen; C1-C8alkyl; C1-C8alkyl substituted with hydroxy, mercapto, C1-C4alkoxy or C1-C4alkylthio: C3-C8alkenyl; C3-C8alkynyl; C3-C8cycloalkyl; C3-C8cycloalkyl-C1-C4alkyl; or the two groups R2 and R3 together with the carbon atom to which they are bonded form a three- to eight-membered hydrocarbon ring;
    • R4, R5, R6 and R7 are each independently hydrogen or C1-C4alkyl;
      Figure US06864392-20050308-C00003
    • R11, R12, R14, R15 and R17 are each independently hydrogen or C1-C4alkyl,
    • R13 is C4-C12alkyl; C1-C12halogenalkyl; C3-C8cycloalkyl; optionally substituted aryl or optionally substituted heteroaryl,
    • R16 is optionally substituted aryl or optionally substituted heteroaryl, and
    • Z is oxygen, sulfur —CR18R19— or —NR20—, wherein R18, R19 and R20 independently of each other are hydrogen or C1-C4alkyl.
In the above definition aryl includes aromatic hydrocarbon rings like phenyl, naphthyl, anthracenyl, phenanthrenyl, with phenyl being preferred.
Heteroaryl stands for aromatic ring systems comprising mono-, bi- or tricyclic systems wherein at least one oxygen, nitrogen or sulfur atom is present as a ring member. Examples are furyl, thienyl, pyrrolyl, imidazolyl, pyrazolyl, thiazolyl, isothiazolyl, oxazolyl, isoxazolyl, oxadiazolyl, thiadiazolyl, triazolyl, tetrazolyl, pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, triazinyl, tetrazinyl, indolyl, benzothiophenyl, benzofuranyl, benzimidazolyl, indazolyl, benzotriazolyl, benzothiazolyl, benzoxazolyl, quinolinyl, isoquinolinyl, phthalazinyl, quinoxalinyl, quinazolinyl, cinnolinyl and naphthyridinyl.
The above aryl and heteroaryl groups may carry one or more identical or different substituents. Normally not more than three substituents are present at the same time. Examples of substituents of aryl or heteroaryl groups are: alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkyl-alkyl, phenyl and phenyl-alkyl, it being possible in turn for all of the preceding groups to carry one or more identical or different halogen atoms; alkoxy; alkenyloxy; alkynyloxy; alkoxyalkyl; halogenalkoxy, alkylthio; halogenalkylthio; alkyl sulfonyl; formyl; alkanoyl; hydroxy; halogen; cyano; nitro; amino; alkylamino; dialkyl amino; carboxy; alkoxycarbonyl; alkenyloxycarbonyl; alkynyloxycarbonyl.
In the above definitions “halogen” or the prefix “halo” includes fluorine, chlorine, bromine and iodine.
The alkyl, alkenyl and alkynyl radicals may be straight-chain or branched. This applies also to the alkyl, alkenyl or alkynyl parts of other alkyl-, alkenyl- or alkynyl-containing groups.
Depending upon the number of carbon atoms mentioned, alkyl on its own or as part of another substituent is to be understood as being, for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl and the isomers thereof, for example isopropyl, isobutyl, tert-butyl or sec-butyl, isopentyl or tert-pentyl.
Cycloalkyl is, depending upon the number of carbon atoms mentioned, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl.
Depending upon the number of carbon atoms mentioned, alkenyl as a group or as a structural element of other groups is to be understood as being, for example, ethenyl, allyl, 1-propenyl, buten-2-yl, buten-3-yl, penten-1-yl, penten-3-yl, hexen-1-yl, 4-methyl-3-pentenyl or 4-methyl-3-hexenyl.
Alkynyl as a group or as a structural element of other groups is, for example, ethynyl, propyn-1-yl, propyn-2-yl, butyn-1-yl, butyn-2-yl, 1-methyl-2-butynyl, hexyn-1-yl, 1-ethyl-2-butynyl or octyn-1-yl.
A halogenalkyl group may contain one or more (identical or different) halogen atoms, and for example may stand for CHCl2, CH2F, CCl3, CH2Cl, CHF2, CF3, CH2CH2Br, C2Cl5, CH2Br, CHClBr, CF3CH2, etc.
Where R2 and R3 together with the carbon atom to which they are attached form a hydrocarbon ring the ring corresponds to cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane or cyclooctane.
Where R9 and R10 together with the nitrogen atom to which they are attached form a ring system the ring corresponds to pyrrolidine or piperidine.
The presence of at least one asymmetric carbon atom and/or at least one asymmetric oxidized sulfur atom in the compounds of formula I means that the compounds may occur in optically isomeric forms. As a result of the presence of a possible aliphatic C═C double bond, geometric isomerism may also occur. Formula I is intended to include all those possible isomeric forms and mixtures thereof.
Preferred subgroups of compounds of formula I are those wherein
    • n is one; or
    • R1 is C1-C12alkyl, C1-C12alkyl substituted with C1-C4alkoxy, C1-C4alkylthio, or C1-C4alkylsulfonyl; C3-C8cycloalkyl; C2-C12alkenyl; C2-C12alkynyl; C1-C12halogenalkyl; or a group NR9R10 wherein R9 and R10 are each independently of the other hydrogen or C1-C6alkyl, or together are tetra- or penta-methylene; or
    • R1 is C1-C12alkyl, C2-C12alkenyl; C1-C12halogenalkyl; or a group NR9R10 wherein R9 and R10 are each independently of the other hydrogen or C1-C6alkyl; or
    • R1 is C1-C4alkyl, C2-C4alkenyl; C1-C4halogenalkyl; or C1-C2dialkylamino; or
    • R1 is C1-C4alkyl, vinyl; C1-C4halogenalkyl; or dimethylamino; or
    • R2 is hydrogen and R3 is C1-C8alkyl, C1-C8alkyl optionally substituted by hydroxy, C1-C4-alkoxy, mercapto or C1-C4alkylthio; C3-C8alkenyl; C3-C8alkynyl; C3-C8cycloalkyl or C3-C8cycloalkyl-C1-C4alkyl; or
    • R2 is hydrogen and R3 is C1-C4alkyl; C3-C4alkenyl or cyclopropyl; or
    • R2 is hydrogen and R3 is C3-C4alkyl; allyl or cyclopropyl; or
    • R2 is hydrogen and R3 is isopropyl; or
    • R4 is hydrogen, methyl or ethyl; or
    • R4 is hydrogen or methyl; or
    • R4 is hydrogen; or
    • R5, R6 and R7 are each independently hydrogen or methyl; or
    • R5, R6 and R7 are each hydrogen; or
    • R11, R12, R14, R15 and R17 are each independently hydrogen or methyl; or
    • R11, R12, R14, R15 and R17 are each hydrogen; or
    • R13 is C4-C12alkyl; C1-C12halogenalkyl; C3-C8cycloalkyl; optionally substituted aryl or optionally substituted heteroaryl consisting of one or two condensed five or six membered rings with 1 to 4 identical or different heteroatoms selected from oxygen, nitrogen or sulfur; or
    • R13 is C4-C12alkyl; C1-C12halogenalkyl; C3-C8cycloalkyl; phenyl, naphthyl, furyl, thienyl, pyrrolyl, imidazolyl, pyrazolyl, thiazolyl, oxazolyl, isoxazolyl, thiazolyl, pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, triazinyl, indolyl, benzothiophenyl, benzofuranyl, benzimidazolyl, benzthiazolyl, benzoxazolyl or quinolyl with each of the aromatic ring being optionally substituted by 1 to 3 substituents selected from the group consisting of C1-C8alkyl, C2-C8alkenyl, C2-C8alkynyl, C3-C8cycloalkyl, C3-C8cycloalkyl-C1-C4alkyl, phenyl, phenyl-C1-C4alkyl wherein the hydrogens of all these substituents may be optionally substituted by one or more identical or different halogen atoms; C1-C8alkoxy, C3-C8alkenyloxy, C3-C8alkynyloxy, C1-C8alkoxy-C1-C4alkyl, C1-C8halogenalkoxy, C1-C8alkylthio, C1-C8halogenalkylthio, C1-C8alkylsulfonyl, formyl, C2-C8alkanoyl, hydroxy, halogen, cyano, nitro, amino and C1-C8alkylamino, C1-C8dialkylamino, carboxy, C1-C8alkoxycarbonyl, C1-C8alkenyloxycarbonyl and C1-C8alkynyloxycarbonyl; or
    • R13 is C4-C12alkyl; C1-C1-halogenalkyl; C3-C8cycloalkyl; phenyl, naphthyl, thienyl, pyridyl, pyrimidinyl, triazinyl, or quinolyl with each of the aromatic ring being optionally substituted by 1 to 3 substituents selected from the group consisting of C1-C8-alkyl, C2-C8alkenyl, wherein the hydrogens of all these substituents may be optionally substituted by one or more identical or different halogen atoms; C1-C8alkoxy, C1-C8halogenalkoxy, C1-C8alkylthio, C1-C8halogenalkylthio, halogen, cyano, nitro and C1-C8alkoxycarbonyl; or
    • R13 is C4-C8alkyl; C1-C6halogenalkyl; C3-C8cycloalkyl; phenyl, pyridyl, with each of the aromatic ring being optionally substituted by 1 to 3 substituents selected from the group consisting of C1-C8alkyl, C1-C8halogenalkyl, C1-C8alkoxy, C1-C8halogenalkoxy, C1-C8alkylthio, C1-C8halogenalkylthio, halogen, cyano, nitro and C1-C8alkoxycarbonyl; or
    • R16 is optionally substituted aryl or optionally substituted heteroaryl consisting of one or two condensed five or six membered rings with 1 to 4 identical or different heteroatoms selected from oxygen, nitrogen or sulfur; or
    • R16 is phenyl, naphthyl, furyl, thienyl, pyrrolyl, imidazolyl, pyrazolyl, thiazolyl, oxazolyl, isoxazolyl, thiazolyl, pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, triazinyl, indolyl, benzothiophenyl, benzofuranyl, benzimidazolyl, benzthiazolyl, benzoxazolyl or quinolyl with each of the aromatic ring being optionally substituted by 1 to 3 substituents selected from the group consisting of C1-C8alkyl, C2-C8alkenyl, C2-C8alkynyl, C3-C8-cycloalkyl, C3-C8cycloalkyl-C1-C4alkyl, phenyl, phenyl-C1-C4alkyl wherein the hydrogens of all these substituents may be optionally substituted by one or more identical or different halogen atoms; C1-C8alkoxy, C3-C8alkenyloxy, C3-C8alkynyloxy, C1-C8alkoxy-C1-C4alkyl, C1-C8halogenalkoxy, C1-C8alkylthio, C1-C8halogenalkylthio, C1-C8alkylsulfonyl, formyl, C2-C8alkanoyl, hydroxy, halogen, cyano, nitro, amino, C1-C8alkylamino, C1-C8dialkylamino, carboxy, C1-C8alkoxycarbonyl, C1-C8alkenyloxycarbonyl and C1-C8alkynyloxycarbonyl; or
    • R16 is phenyl, naphthyl, thienyl, pyridyl, pyrimidinyl, triazinyl, or quinolyl with each of the aromatic ring being optionally substituted by 1 to 3 substituents selected from the group consisting of C1-C8alkyl, C2-C8alkenyl, wherein the hydrogens of all these substituents may be optionally substituted by one or more identical or different halogen atoms; C1-C8alkoxy, C1-C8halogenalkoxy, C1-C8alkylthio, C1-C8halogenalkylthio, halogen, cyano, nitro and C1-C8alkoxycarbonyl; or
    • R16 is phenyl, pyridyl, with each of the aromatic ring being optionally substituted by 1 to 3 substituents selected from the group consisting of C1-C8alkyl, C1-C8halogenalkyl, C1-C8alkoxy, C1-C8halogenalkoxy, C1-C8alkylthio, C1-C8-halogenalkylthio, halogen, cyano, nitro and C1-C8alkoxycarbonyl; or
    • Z is oxygen, sulfur or —CH2—; or
    • Z is oxygen.
Further preferred subgroups of the compounds of formula I are those wherein
  • 1) R1 is C1-C12alkyl, C1-C12alkyl substituted with C1-C4alkoxy, C1-C4alkylthio, or C1-C4alkylsulfonyl; C3-C8cycloalkyl; C2-C12alkenyl; C2-C12alkynyl; C1-C12halogenalkyl; or a group NR9R10 wherein R9 and R10 are each independently of the other hydrogen or C1-C6alkyl, or together are tetra- or penta-methylene;
    • R2 is hydrogen and R3 is C1-C8alkyl; C1-C8alkyl substituted with hydroxy, mercapto, C1-C4alkoxy or C1-C4alkylthio; C3-C8alkenyl; C3-C8alkynyl; C3-C8cycloalkyl; C3-C8cycloalkyl-C1-C4alkyl;
    • R13 is C4-C12-alkyl; C1-C12-halogenalkyl; C3-C8cycloalkyl; optionally substituted aryl or optionally substituted heteroaryl consisting of one or two condensed five or six membered rings with 1 to 4 identical or different heteroatoms selected from oxygen, nitrogen or sulfur; and
    • R16 is optionally substituted aryl or optionally substituted heteroaryl consisting of one or two condensed five or six membered rings with 1 to 4 identical or different heteroatoms selected from oxygen, nitrogen or sulfur; or
  • 2) n is one;
    • R1 is C1-C12alkyl, C2-C12alkenyl; C1-C12halogenalkyl; or a group NR9R10 wherein R9 and R10 are each independently of the other hydrogen or C1-C6alkyl;
    • R2 is hydrogen and R3 is C1-C4alkyl; C3-C4alkenyl or cyclopropyl;
    • R4 is hydrogen, methyl or ethyl; or
    • R5, R6, R7, R11, R12, R14, R15 and R17 are each independently hydrogen or methyl;
    • R13 is C4-C12alkyl; C1-C12-halogenalkyl; C3-C8-cycloalkyl; phenyl, naphthyl, furyl, thienyl, pyrrolyl, imidazolyl, pyrazolyl, thiazolyl, oxazolyl, isoxazolyl, thiazolyl, pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, triazinyl, indolyl, benzothiophenyl, benzofuranyl, benzimidazolyl, benzthiazolyl, benzoxazolyl or quinolyl with each of the aromatic ring being optionally substituted by 1 to 3 substituents selected from the group consisting of C1-C8alkyl, C2-C8alkenyl, C2-C8alkynyl, C3-C8cycloalkyl, C3-C8cycloalkyl -C1-C4alkyl, phenyl, phenyl-C1-C4alkyl wherein the hydrogens of all these substituents may be optionally substituted by one or more identical or different halogen atoms; C1-C8alkoxy, C3-C8alkenyloxy, C3-C8alkynyloxy, C1-C8alkoxy-C1-C4alkyl, C1-C8halogenalkoxy, C1-C8alkylthio, C1-C8halogenalkylthio, C1-C8alkylsulfonyl, formyl, C2-C8alkanoyl, hydroxy, halogen, cyano, nitro, amino and C1-C8alkylamino, C1-C8-dialkylamino, carboxy, C1-C8-alkoxycarbonyl, C1-C8-alkenyloxycarbonyl and C1-C8alkynyloxycarbonyl;
    • R16 is phenyl, naphthyl, furyl, thienyl, pyrrolyl, imidazolyl, pyrazolyl, thiazolyl, oxazolyl, isoxazolyl, thiazolyl, pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, triazinyl, indolyl, benzothiophenyl, benzofuranyl, benzimidazolyl, benzthiazolyl, benzoxazolyl or quinolyl with each of the aromatic ring being optionally substituted by 1 to 3 substituents selected from the group consisting of C1-C8-alkyl, C2-C8alkenyl, C2-C8alkynyl, C3-C8cycloalkyl, C3-C8cycloalkyl-C1-C4alkyl, phenyl, phenyl-C1-C4alkyl wherein the hydrogens of all these substituents may be optionally substituted by one or more identical or different halogen atoms; C1-C8alkoxy, C3-C8alkenyloxy, C3-C8alkynyloxy, C1-C8alkoxy-C1-C4alkyl, C1-C8halogenalkoxy, C1-C8alkylthio, C1-C8halogenalkylthio, C1-C8alkylsulfonyl, formyl, C2-C8alkanoyl, hydroxy, halogen, cyano, nitro, amino and C1-C8alkylamino, C1-C8dialkylamino, carboxy, C1-C8alkoxycarbonyl, C1-C8alkenyloxycarbonyl and C1-C8alkynyloxycarbonyl; and
    • Z is oxygen, sulfur or —CH2—; or
  • 3) n is one;
    • R1 is C1-C4alkyl, C2-C4alkenyl; C1-C4halogenalkyl; or C1-C2-dialkylamino;
    • R2 is hydrogen and R3 is C3-C4alkyl; allyl or cyclopropyl;
    • R4 is hydrogen or methyl;
    • R5, R6, R7, R11, R12, R14, R15 and R17 are each hydrogen;
    • R13 is C4-C12alkyl; C1-C12halogenalkyl; C3-C8cycloalkyl; phenyl, naphthyl, thienyl, pyridyl, pyrimidinyl, triazinyl, or quinolyl with each of the aromatic ring being optionally substituted by 1 to 3 substituents selected from the group consisting of C1-C8alkyl, C2-C8alkenyl, wherein the hydrogens of all these substituents may be optionally substituted by one or more identical or different halogen atoms; C1-C8alkoxy, C1-C8halogenalkoxy, C1-C8alkylthio, C1-C8halogenalkylthio, halogen, cyano, nitro and C1-C8alkoxycarbonyl;
    • R16 is phenyl, naphthyl, thienyl, pyridyl, pyrimidinyl, triazinyl, or quinolyl with each of the aromatic ring being optionally substituted by 1 to 3 substituents selected from the group consisting of C1-C8alkyl, C2-C8alkenyl, wherein the hydrogens of all these substituents may be optionally substituted by one or more identical or different halogen atoms; C1-C8alkoxy, C1-C8halogenalkoxy, C1-C8alkylthio, C1-C8halogenalkylthio, halogen, cyano, nitro and C1-C8alkoxycarbonyl; and
    • Z is oxygen, sulfur or —CH2—; or
  • 4) n is one;
    • R1 is C1-C4alkyl, vinyl; C1-C4halogenalkyl; or dimethylamino;
    • R2 is hydrogen and R3 is isopropyl;
    • R4, R5, R6, R7, R11, R12, R14, R15 and R17 are each hydrogen;
    • R13 is C4-C8alkyl; C1-C6halogenalkyl; C3-C8cycloalkyl; phenyl, pyridyl, with each of the aromatic ring being optionally substituted by 1 to 3 substituents selected from the group consisting of C1-C8alkyl, C1-C8halogenalkyl, C1-C8alkoxy, C1-C8halogenalkoxy, C1-C8alkylthio, C1-C8-halogenalkylthio, halogen, cyano, nitro and C1-C8alkoxycarbonyl;
    • R16 is phenyl, pyridyl, with each of the aromatic ring being optionally substituted by 1 to 3 substituents selected from the group consisting of C1-C8alkyl, C1-C8halogenalkyl, C1-C8alkoxy, C1-C8halogenalkoxy, C1-C8alkylthio, C1-C8halogenalkylthio, halogen, cyano, nitro and C1-C8alkoxycarbonyl; and
    • Z is oxygen.
Preferred individual compounds are:
  • N-(2-{4-[3-(4-chloro-phenyl))-prop-2-ynyloxy]-phenyl}-ethyl)-2-methanesulfonyalmino-3-methyl-butyramide,
  • N-(2-{4-[3-(4-fluoro-phenyl)-prop-2-ynyloxy]-phenyl}-ethyl)-2-methanesulfonylamino-3-methyl-butyramide,
  • N-(2-{4-[3-(4-bromo-phenyl)-prop-2-ynyloxy]-phenyl}-ethyl)-2-methanesulfonylamino-3-methyl-butyramide,
  • N-(2-{4-[3-(p-tolyl)-prop-2-ynyloxy]-phenyl}-ethyl)-2-methanesulfonylamino-3-methyl-butyramide,
  • N-{2-[4-(3-cyclopropyl-prop-2-ynyloxy)-phenyl]-ethyl}-2-methanesulfonylamino-3-methyl-butyramide,
  • N-(2-{4-[3-(4-chloro-phenyl)-prop-2-ynyloxy]-phenyl}-ethyl)-2-ethanesulfonylamino-3-methyl-butyramide,
  • N-(2-{4-[3-(4-fluoro-phenyl)-prop-2-ynyloxy]-phenyl}-ethyl)-2-ethanesulfonylamino-3-methyl-butyramide,
  • N-(2-{4-[3-(4-bromo-phenyl)-prop-2-ynyloxy]-phenyl}-ethyl)-2-ethanesulfonylamino-3-methyl-butyramide,
  • N-(2-{4-[3-(p-tolyl)-prop-2-ynyloxy]-phenyl}-ethyl)-2-ethanesulfonylamino-3-methyl-butyramide, and
  • N-{2-[4-(3-cyclopropyl-prop-2-ynyloxy)-phenyl]-ethyl}-2-ethanesulfonylamino-3-methyl-butyramide.
Certain α-sulfin- and α-sulfonamino acid derivatives having a different kind of molecular structure have already been proposed for controlling plant-destructive fungi (for example in WO 95/030651, WO 97/14677, WO 98/38160, WO 98/38161 and WO 99/07674).
However, the activity of the known compounds is not always satisfactory in all aspects of agricultural needs. Surprisingly, with the compound structure of formula I, a new kind of microbiocides have been found showing an improved systemic activity in plants against phytopathogenic microorganisms, especially fungi.
The α-sulfin- and α-sulfonamino acid amides of formula I may be obtained according to one of the following processes:
a)
Figure US06864392-20050308-C00004
An amino acid of formula II or a carboxy-activated derivative of an amino acid of formula II wherein R1, n, R2 and R3 are as defined for formula I is reacted with an amine of formula III wherein R4, R5, R6, R7 and R8 are as defined above optionally in the presence of a base and optionally in the presence of a diluting agent (step B).
Carboxy-activated derivatives of the amino acid of formula II encompasses all compounds having an activated carboxyl group like an acid halide, such as an acid chloride, like symmetrical or mixed anhydrides, such as mixed anhydrides with O-alkylcarbonates, like activated esters, such as p-nitrophenylesters or N-hydroxysuccinimidesters, as well as in situ produced activated forms of the amino acid of formula II by condensating agents, such as dicyclohexylcarbodiimide, carbonyldiimidazol, benzotriazol-1-yloxy-tris (dimethylamino)phosphonium hexafluorophosphate, O-benzotriazol-1-yl N,N,N′,N′-bis(penta methylene)uronium hexafluorophosphate, O-benzotriazol-1-yl N,N,N′,N′-bis(tetramethylene)uronium hexafluorophosphate, O-benzotriazol-1-yl N,N,N′,N′-tetramethyluronium hexafluoro-phosphate or benzotriazol-1-yloxy-tripyrrolidino phosphonium hexafluorophosphate. The mixed anhydrides of the amino acids of the formula II may be prepared by reaction of an amino acid of formula II with chloroformic acid esters like chloroformic acid alkylesters, such as ethyl chloroformate or isobutyl chloroformate, optionally in the presence of an organic or inorganic base like a tertiary amine, such as triethylamine, N,N-diisopropyl-ethylamine, pyridine, N-methyl-piperidine or N-methyl-morpholine.
The present reaction is preferably performed in an inert solvent like aromatic, non-aromatic or halogenated hydrocarbons, such as chlorohydrocarbons e.g. dichloromethane or toluene; ketones, e.g. acetone; esters, e.g. ethyl acetate; amides, e.g. N,N-dimethylformamide; nitriles e.g. acetonitrile; or ethers e.g. diethylether, tert-butyl-methylether, dioxane or tetrahydrofurane or water. It is also possible to use mixtures of these solvents. The reaction is preformed optionally in the presence of an organic or inorganic base like a tertiary amine, e.g. triethylamine, N,N-diisopropyl-ethylamine, pyridine, N-methyl-piperidine or N-methyl-morpholine, like a metal hydroxide or a metal carbonate, preferentially an alkali hydroxide or an alkali carbonate, such as lithium hydroxide, sodium hydroxide or potassium hydroxide at temperatures ranging from −80° C. to +150° C., preferentially at temperatures ranging from −40° C. to +40° C.
The compounds of formula II may be prepared by reaction of an amino acid of formula IV where R2 and R3 are as defined for formula I with a sulfonyl halide or a sulfinyl halide of formula V where R1 and n have the same meanings as defined above and where X is halide, preferentially chlorine or bromine (step A).
The reaction may be performed in an inert solvent like aromatic, non-aromatic or halogenated hydrocarbons, such as chlorohydrocarbons, e.g. dichloromethane or toluene; ketones, e.g. acetone; esters, e.g. ethyl acetate; ethers, e.g. diethylether, tert-butyl-methylether, dioxane or tetrahydrofurane or water. It is also possible to use mixtures of these solvents. The reaction is performed optionally in the presence of an organic or inorganic base like a tertiary amine, such as triethylamine, N,N-diisopropyl-ethylamine, pyridine, N-methyl-piperidine or N-methyl-morpholine, like a metal hydroxide or a metal carbonate, preferentially an alkali hydroxide or an alkali carbonate, such as lithium hydroxide, sodium hydroxide or potassium hydroxide at temperatures ranging from −80° C. to +150° C., preferentially at temperatures ranging from −40° C. to +40° C.
b)
Figure US06864392-20050308-C00005
The compounds of formula I may also be prepared by reaction of an amino acid derivative of formula VI wherein R2, R3, R4, R5, R6, R7 and R8 are as defined for formula I with a sulfonyl halide or a sulfinyl halide of formula V wherein R1 and n are as defined for formula I and X is halide, preferentially chlorine or bromine (step C). The reaction is performed in the same manner as described for step A.
c)
Figure US06864392-20050308-C00006
The compounds of formula I may also be prepared by reaction of a phenol of formula VII wherein R1, n, R2, R3, R4, R5, R6 and R7 are as defined for formula I with a compound of formula VIII wherein R8 is as defined for formula I and Y is a leaving group like a halide such as a chloride or bromide or a sulfonic ester such as a tosylate, mesylate or triflate (step D). The reaction may be performed in an inert solvent like aromatic, non-aromatic or halogenated hydrocarbons, such as chlorohydrocarbons e.g. dichloromethane or toluene; ketones e.g. acetone or 2-butanone; esters, e.g. ethyl acetate; ethers, e.g. diethylether, tert-butyl-methylether, dioxane or tetrahydrofurane, amides, e.g. dimethylformamide, nitriles, e.g. acetonitrile, alcohols, e.g. methanol, ethanol, isopropanol, n-butanol or tert-butanol, sulfoxides e.g. dimethylsulfoxide or water. It is also possible to use mixtures of these solvents. The reaction is performed optionally in the presence of an organic or inorganic base like a tertiary amine, such as triethylamine, N,N-diisopropyl-ethylamine, pyridine, N-methyl-piperidine or N-methyl-morpholine, like a metal hydroxide, a metal carbonate or a metal alkoxide, preferentially an alkali hydroxide, an alkali carbonate or an alkali alkoxide, such as lithium hydroxide, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium methoxide, potassium methoxide, sodium ethoxide, potassium ethoxide, sodium tert-butoxide or potassium tert-butoxide at temperatures ranging from −80° C. to +200° C., preferentially at temperatures ranging from 0° C. to +120° C.
d)
Figure US06864392-20050308-C00007
The compounds of formula Ia may also be prepared via formula IX wherein R1, n, R2, R3, R4, R5, R6, R7, R11, R12 and R13 are defined for formula I by reacting of a phenol of formula VII wherein R1, n, R2, R3, R4, R5, R6 and R7 are as defined for formula I with a compound of formula VIIIa wherein R11, R12 and R13 are as defined for formula I and Y is a leaving group like a halide such as a chloride or bromide or a sulfonic ester such as a tosylate, mesylate or triflate (step E).
The reaction is performed in the same manner as described for step D.
The compounds of formula Ia R11, R12 and R13 is as defined for formula I may be prepared by reaction of compounds of formula IX with hydrogen.
The reaction is performed in a solvent like ethers, e.g. diethylether, dioxane or tetrahydrofuran, or like alcohols, e.g. methanol or ethanol, or water in the presence of transition metals or transition metal salts, e.g. nickel, cobalt, palladium, platinum or rhodium, optionally in the presence of bases, e.g. ammonia, or in the presence of salts, e.g. barium sulfate, at temperatures ranging from −20° C. to +160° C. and at pressures ranging from 1 to 200 bar.
aa) The intermediate amines of formula III may be obtained by one of the following processes:
Figure US06864392-20050308-C00008
Figure US06864392-20050308-C00009
Step 1 is the alkylation of a phenol with a compound of formula VIII. The reaction is performed in the same manner as described for procedure c).
Step 2 is the reaction of an aromatic aldehyde with nitromethane. This reaction is performed in a solvent like an organic carboxylic acids, e.g. acetic acid optionally in the presence of the ammonium salt of this carboxylic acid, e.g. ammonium acetate at temperatures ranging from 0° C. to +200° C.
Step 3 is the reduction of an unsaturated nitrogen-compound. This reaction is performed in a solvent like an ether, e.g. diethylether, dioxane or tetrahydrofuran, or an alcohol, e.g. methanol, ethanol or isopropanol, with borohydride, with a boron-complex, e.g. the complex of borohydride with tetrahyrofuran, with an alkaliborohydride, with an alkalialuminiumhydride, e.g. lithiumaluminiumhydride, with aluminiumhydride, with an aluminiumalkoxyhydride or with hydrogen optionally in the presence of a transition metal, a transition metal salt or a transition metal complex, e.g. nickel, cobalt, palladium, platinium or rhodium at temperatures ranging from −50° C. to +200° C.
Step 4 is the reaction of an aldehyde or a ketone of formula XXIII with hydroxylamine or with a salt of hydroxylamine. This reaction is performed in a solvent like an alcohol, e.g. methanol, ethanol or isopropanol, like an ether, e.g. diethylether, dioxane or tetrahydrofuran, like an amide, e.g. dimethylformamide, or in water or in a mixture of these solvents optionally in the presence of an organic or inorganic base like a tertiary amine, e.g. triethylamine, like a heterocyclic compound containing nitrogen, e.g. pyridine, or like an alkalicarbonate, e.g. sodium carbonate or potassium carbonate, at temperatures ranging from −20° C. to +150° C.
Step 5 is the exchange of hydroxy by cyanide. This reaction is performed in an organic solvent like an amide, e.g. dimethylformamide using a metal cyanide like an alkali cyanide, e.g. sodium cyanide or potassium cyanide, at temperatures ranging from 0° C. to +200° C.
Step 6 is the hydrolysis of an alkyl ester. This reaction is performed in a solvent like an alcohol, e.g. methanol, ethanol or isopropanol, like an ether, e.g. diethylether, dioxane or tetrahydrofuran, like a halogenated hydrocarbon, e.g. dichloromethane, or water or in a mixture of these solvents optionally in the presence of an alkali hydroxide, e.g. lithium hydroxide, sodium hydroxide or potassium hydroxide, or optionally in the presence of an acid, e.g. hydrogen chloride, sulfuric acid or trifluoroacetic acid at temperatures ranging from −20° C. to +160° C.
Step 7 is the reaction of a carboxylic acid or the activated form of this carboxylic acid with hydrogen azide or an azide-salt. An activated form of a carboxylic acid can be the acid halogenide, e.g. acid chloride, a symmetric or a mixed anhydride. Azide-salts can be alkali azides, e.g. sodium azide. The reaction is performed in a solvent like a hydrocarbon, e.g. toluene or xylene, like a halogenated hydrocarbon, e.g. chloroform, like an ether, e.g. dioxane, like a ketone, e.g. acetone or 2-butanone, like an alcohol, e.g. methanol, ethanol or tert-butanol, or water or in a mixture of these solvents optionally in the presence of an acid like an inorganic acid, e.g. sulfuric acid or hydrogen chloride at temperatures ranging from −40° C. to +200° C.
In a preferred form the compounds of formula XXVI are prepared starting from compounds of the formula XXV by applying step 5 and step 1 in the same pot.
bb) Amines of formula VI can be obtained by the following process:
Figure US06864392-20050308-C00010

wherein R is lower alkyl or optionally substituted benzyl.
Step 8 is the amidation of an carbamate-protected amino acid of formula XXXIII with an amine of formula XXXIV. The reaction is performed in the same manner as described for step A.
Step 9 is the alkylation of a phenol of formula XXXV with an compound of formula VIII. The reaction is performed in the same manner as described for step D.
Step 10 is the hydrolysis of a carbamate of formula XXXVI. The reaction is performed in a solvent like hydrocarbons, e.g. toluene, like halogenated hydrocarbons, e.g. dichloromethane, like ketones, e.g. acetone, like esters, e.g. ethyl acetate, like ethers, e.g. dioxane or tetrahydrofuran, or like water or in mixtures of these solvents optionally in the presence of an organic acid like carboxylic acid, e.g. trifluoroacetic acid, or like a sulfonic acid, e.g. methanesulfonic acid or toluenesulfonic acid, or in the presence of an inorganic acid, e.g. hydrogen chloride or sulfuric acid, at temperatures ranging from −40° C. to +160° C.
The compounds of formula I are oils or solids at room temperature and are distinguished by valuable microbiocidal properties. They can be used in the agricultural sector or related technical fields preventively and curatively for the control of plant-destructive microorganisms. The compounds of formula I according to the invention are distinguished at low rates of concentration not only by outstanding microbiocidal, especially fungicida I, activity but also by being especially well tolerated by the treated crop plants.
Surprisingly, it has now been found that for practical purposes the compounds of formula I have a very advantageous biocidal spectrum in the control of phytopathogenic microorganisms, especially fungi. With the compounds of formula I it is possible to inhibit or destroy phytopathogenic microorganisms that occur on various crops of useful plants or on parts of such plants (fruit, blossom, leaves, stems, tubers, roots), while parts of the plants which grow later also remain protected, for example, against phyto pathogenic fungi.
The novel compounds of formula I prove to be effective against specific genera of the fungus classes Fungi imperfecti (e.g. Cercospora), Basidio mycetes (e.g. Puccinia) and Ascomycetes (e.g. Erysiphe and Venturia) and especially against Oomycetes (e.g. Plasmopara, Peronospora, Pythium and Phytophthora). They therefore represent in plant protection a valuable addition to the compositions for controlling phyto pathogenic fungi. The compounds of formula I can also be used as coatings or dressings for protecting seed (fruit, tubers, grains) and plant cuttings from fungal infections and against phyto pathogenic fungi that occur in the soil.
The invention relates also to compositions comprising compounds of formula I as active ingredient, especially plant-protecting compositions, and to the use thereof in the agricultural sector or related fields.
In addition, the present invention includes the preparation of those compositions, wherein the active ingredient is homogeneously mixed with one or more of the substances or groups of substances described herein. Also included is a method of treating plants which is distinguished by the application of the novel compounds of formula I or of the novel compositions.
Target crops to be protected within the scope of this invention comprise, for example, the following species of plants: cereals (wheat, barley, rye, oats, rice, maize, sorghum and related species); beet (sugar beet and fodder beet); pomes, stone fruit and soft fruit (apples, pears, plums, peaches, almonds, cherries, strawberries, raspberries and blackberries); leguminous plants (beans, lentils, peas, soybeans); oil plants (rape, mustard, poppy, olives, sunflowers, coconut, castor oil plants, cocoa beans, groundnuts); cucurbitaceae (marrows, cucumbers, melons); fibre plants (cotton, flax, hemp, jute); citrus fruit (oranges, lemons, grapefruit, mandarins); vegetables (spinach, lettuce, asparagus, cabbages, carrots, onions, tomatoes, potatoes, paprika); lauraceae (avocado, cinnamon, camphor) and plants such as tobacco, nuts, coffee, sugar cane, tea, pepper, vines, hops, bananas and natural rubber plants, and also ornamentals.
The compounds of formula I are normally used in the form of compositions and can be applied to the area or plant to be treated simultaneously or in succession with other active ingredients. Those other active ingredients may be fertilisers, micronutrient donors or other preparations that influence plant growth. It is also possible to use selective herbicides or insecticides, fungicides, bactericides, nematicides, molluscicides or mixtures of several of those preparations, if desired together with further carriers, surfactants or other application-promoting adjuvants customarily employed in formulation technology.
The compounds of formula I can be mixed with other fungicides, resulting in some cases in unexpected synergistic activities.
Mixing components which are particularly preferred are azoles such as azoles, such as azaconazole, bitertanol, bromuconazole, cyproconazole, difenoconazole, diniconazole, epoxiconazole, fenbuconazole, fluquinconazole, flusilazole, flutriafol, hexaconazole, imazalil, imibenconazole, ipconazole, metconazole, myclobutanil, pefurazoate, penconazole, pyrifenox, prochloraz, propiconazole, tebuconazole, tetraconazole, triadimefon, triadimenol, triflumizole, triticonazole; pyrimidinyl carbinols, such as ancymidol, fenarimol, nuarimol; 2-amino-pyrimidines, such as bupirimate, dimethirimol, ethirimol; morpholines, such as dodemorph, fenpropidine, fenpropimorph, spiroxamine, tridemorph; anilinopyrimidines, such as cyprodinil, mepanipyrim, pyrimethanil; pyrroles, such as fenpiclonil, fludioxonil; phenylamides, such as benalaxyl, furalaxyl, metalaxyl, R-metalaxyl, ofurace, oxadixyl; benzimidazoles, such as benomyl, carbendazim, debacarb, fuberidazole, thiabendazole; dicarboximides, such as chlozolinate, dichlozoline, iprodione, myclozoline, procymidone, vinclozolin; carboxamides, such as carboxin, fenfuram, flutolanil, mepronil, oxycarboxin, thifluzamide; guanidines, such as guazatine, dodine, iminoctadine; strobilurines, such as azoxystrobin, kresoxim-methyl, metominostrobin, SSF-129, CGA 279202 (trifloxystrobin), picoxystrobin; dithiocarbamates, such as ferbam, mancozeb, maneb, metiram, propineb, thiram, zineb, ziram; N-halogenmethylthiophthalimides, such as captafol, captan, dichlofluanid, fluoromide, folpet, tolyfluanid; Cu compounds, such as Bordeaux mixture, copper hydroxide, copper oxychloride, copper sulfate, cuprous oxide, mancopper, oxine-copper; nitrophenol derivatives, such as dinocap, nitrothal-isopropyl; organo-P derivatives, such as edifenphos, iprobenphos, isoprothiolane, phosdiphen, pyrazophos, tolclofos-methyl; various, such as AC382042, acibenzolar-S-methyl, anilazine, blasticidin-S, quinomethionat, chloroneb, chlorothalonil, cymoxanil, dichlone, diclomezine, dicloran, diethofencarb, dimethomorph, dithianon, etridiazole, famoxadone, fenamidone, fenhexamid, fentin, ferimzone, fluazinam, flusulfamide, fosetyl-aluminium, hymexazol, IKF-916, iprovalicarb, kasugamycin, methasulfocarb, MON65500, pencycuron, phthalide, polyoxins, probenazole, propamocarb, pyroquilon, quinoxyfen, quintozene, RH-7281, RPA 407213, BAS 50001 F, sulfur, SYP-Z071, triazoxide, tricyclazole, triforine, validamycin.
Suitable carriers and surfactants may be solid or liquid and correspond to the substances ordinarily employed in formulation technology, such as e.g. natural or regenerated mineral substances, solvents, dispersants, wetting agents, tackifiers, thickeners, binders or fertilisers. Such carriers and additives are described, for example, in WO 95/30651.
A preferred method of applying a compound of formula I, or an agrochemical composition comprising at least one of those compounds, is application to the foliage (foliar application), the frequency and the rate of application depending upon the risk of infestation by the pathogen in question. The compounds of formula I may also be applied to seed grains (coating) either by impregnating the grains with a liquid formulation of the active ingredient or by coating them with a solid formulation.
The compounds of formula I are used in unmodified form or, preferably, together with the adjuvants conventionally employed in formulation technology, and are for that purpose advantageously formulated in known manner e.g. into emulsifiable concentrates, coatable pastes, directly sprayable or dilutable solutions, dilute emulsions, wettable powders, soluble powders, dusts, granules, and by encapsulation in e.g. polymer substances. As with the nature of the compositions, the methods of application, such as spraying, atomising, dusting, scattering, coating or pouring, are chosen in accordance with the intended objectives and the prevailing circumstances.
Advantageous rates of application are normally from 1 g to 2 kg of active ingredient (a.i.) per hectare (ha), preferably from 10 g to 1 kg a.i./ha, especially from 25 g to 750 g a.i./ha. When used as seed dressings, rates of from 0.001 g to 1.0 g of active ingredient per kg of seed are advantageously used.
The formulations, i.e. the compositions, preparations or mixtures comprising the compound(s) (active ingredient(s)) of formula I and, where appropriate, a solid or liquid adjuvant, are prepared in known manner, e.g. by homogeneously mixing and/or grinding the active ingredient with extenders, e.g. solvents, solid carriers and, where appropriate, surface-active compounds (surfactants).
Further surfactants customarily used in formulation technology will be known to the person skilled in the art or can be found in the relevant technical literature.
The agrochemical compositions usually comprise 0.01 to 99% by weight, preferably 0.1 to 95% by weight, of a compound of formula I, 99.99 to 1% by weight, preferably 99.9 to 5% by weight, of a solid or liquid adjuvant, and 0 to 25% by weight, preferably 0.1 to 25% by weight, of a surfactant.
Whereas commercial products will preferably be formulated as concentrates, the end user will normally employ dilute formulations.
The compositions may also comprise further ingredients, such as stabilisers, antifoams, viscosity regulators, binders and tackifiers, as well as fertilisers or other active ingredients for obtaining special effects.
The Examples which follow illustrate the invention described above, without limiting the scope thereof in any way. Temperatures are given in degrees Celsius.
PREPARATION EXAMPLES FOR COMPOUNDS OF FORMULA I Example A1.1 (S)-2-Ethanesulfonylamino-N-(2-{4-[3-(4-chloro-phenyl)-propargyloxy]-phenyl}-ethyl)-3-methyl-butyramide
Figure US06864392-20050308-C00011
A mixture of 1.0 g of (S)-2-ethanesulfonylamino-N-[2-(4-hydroxy-phenyl)-ethyl]-3-methyl-butyramide, 1.3 g of toluene-4-sulfonic acid 3-(4-chloro-phenyl)-prop-2-ynyl ester and 4.9 ml of a 1M solution of sodium methoxide in methanol in 25 ml of methanol is heated to reflux for 2 hours. After cooling 200 ml of water is added. The mixture is extracted with ethyl acetate (2×300 ml). The organic layers are washed with brine (2×100 ml), combined, dried (MgSO4) and evaporated. (S)-N-(2-{4-[3-(4-Chloro-phenyl)-propargyloxy]-phenyl}-ethyl)-2-ethanesulfonylamino-3-methyl-butyramide is obtained which is purified by recrystallization (ethyl acetate/hexane), m.p. 141-142° C.
Analogously to example A1.1 the compounds listed in table A1 are obtained.
    • *) Configuration on the α-C-atom in the amino acid moiety; Ph means phenyl
TABLE A1
Figure US06864392-20050308-C00012
No R1 *) R3 R4 R8 m.p. (° C.)
A1.1 CH3—CH2 (S) (CH3)2CH— H (4-Cl—Ph)—C≡C—CH2 141-142
A1.2 CH3—CH2 (S) (CH3)2CH— H (4-F—Ph)—C≡C—CH2 133-134
A1.3 CH3 (S) (CH3)2CH— H (4-Cl—Ph)—C≡C—CH2 154-155
A1.4 CH3 (S) (CH3)2CH— H (4-F—Ph)—C≡C—CH2 104-105
A1.5 CH3 (S) (CH3)2CH— H (4-Br—Ph)—C≡C—CH2 161-164
A1.6 CH3 (S) (CH3)2CH— H (4-CH3-Ph)—C≡C—CH 2 110-112
A1.7 CH3 (S) (CH3)2CH— H (4-Cl—Ph)—CH═CH—CH2 144-145
A1.8 CH3 (S) (CH3)2CH— H (4-Cl—Ph)—CH2—CH2—CH2 176-177
A1.9 CH3 (S) (CH3)2CH— H (3-CF3—Ph)—CH2 147-153
Example A2.1 (S)-2-Ethanesulfonylamino-N-[2-(4-hydroxy-phenyl)-ethyl]-3-methyl-butyramide
Figure US06864392-20050308-C00013
18.6 g of (S)-N-[2-(4-benzyloxy-phenyl)-ethyl]-2-ethanesulfonylamino-3-methyl-butyramide and 16.8 g of palladium (5% on charcoal) in 400 ml of tetrahydrofuran are shaken under a hydrogen atmosphere at +30 to +−35° C. and at normal pressure for 5 hours. The reaction mixture is filtered and evaporated. (S)-2-ethanesulfonylamino-N-[2-(4-hydroxy-phenyl)-ethyl]-3-methyl-butyramide is obtained in form of an oil [MS (m/e): 329 (M+H)+].
Analogously to example A2.1 the compounds listed in table A2 are obtained.
    • *) Configuration on the α-C-atom in the amino acid moiety; Ph means phenyl
TABLE A2
Figure US06864392-20050308-C00014
No R1 *) R3 R4 m.p. (° C.)
A2.1 CH3—CH2 (S) (CH3)2CH— H Oil
A2.2 CH3 (S) (CH3)2CH— H 120-121
*) Configuration of the amino acid moiety
Example A3.1 (S)-N-[2-(4-Benzyloxy-phenyl)-ethyl]-2-ethanesulfonylamino-3-methyl-butyramide
Figure US06864392-20050308-C00015
15 g of (S)-2-ethanesulfonylamino-3-methyl-butyric acid, 10.3 g of thionyl chloride and N,N-dimethylformamide (2 drops) in toluene (75 ml) are refluxed for 2 hours. The solvent is then evaporated. To the resulting residue 100 ml of toluene is added. The mixture is then evaporated to dryness again. The residue is dissolved in dioxane (100 ml) and added to a mixture of 2-(4-benzyloxy-phenyl)-ethylamine (15.3 g) and triethylamine (7.2 g) in dioxane (100 ml). The reaction mixture is stirred at room temperature over night. Water (400 ml) is added. It is extracted with ethyl acetate (2×500 ml). The organic layers are washed with hydrochloric acid (80 ml, 1M solution) and brine (2×100 ml), dried (MgSO4) and evaporated. (S)-N-[2-(4-Benzyloxy-phenyl)-ethyl]-2-ethanesulfonylamino-3-methyl-butyramide which is purified by recrystallization (ethyl acetate/hexane), m.p. 133-134° C.
Analogously to example A3.1 the compounds listed in table A3 are obtained.
    • *) Configuration on the α-C-atom in the amino acid moiety; Ph means phenyl
TABLE A3
Figure US06864392-20050308-C00016
No R1 *) R3 R4 m.p. (° C.)
A3.1 CH3—CH2 (S) (CH3)2CH— H 133-134
A3.2 CH3 (S) (CH3)2CH— H 153-154
*) Configuration of the amino acid moiety
Analogously to the above Examples the following compounds of Tables 1 to 13 may be prepared. In the tables Ph means phenyl.
TABLE 1
Compounds represented by the Formula I.1 where the combination
of the groups R1, R3 and R8 corresponds
to each row in table A.
I.1
Figure US06864392-20050308-C00017
TABLE 2
Compounds represented by the Formula I.2 where the combination
of the groups R1, R3 and R8 corresponds
to each row in table A.
I.2
Figure US06864392-20050308-C00018
TABLE 3
Compounds represented by the Formula I.3 where the combination
of the groups R1, R3 and R8 corresponds
to each row in table A.
I.3
Figure US06864392-20050308-C00019
TABLE 4
Compounds represented by the Formula I.4 where the combination
of the groups R1, R3 and R8 corresponds
to each row in table A.
I.4
Figure US06864392-20050308-C00020
TABLE 5
Compounds represented by the Formula I.5 where the combination
of the groups R1, R3 and R8 corresponds
to each row in table A.
I.5
Figure US06864392-20050308-C00021
TABLE 6
Compounds represented by the Formula I.6 where the combination
of the groups R1, R3 and R8 corresponds to each
row in table A.
I.6
Figure US06864392-20050308-C00022
TABLE A
No. R1 R3 R8
001 CH3 CH3—CH2 CH3—(CH2 )3—C≡C—CH2
002 CH3—CH2 CH3—CH2 CH3—(CH2 )3—C≡C—CH2
003 (CH3)2N— CH3—CH2 CH3—(CH2 )3—C≡C—CH2
004 CH3—CH2—CH2 CH3—CH2 CH3—(CH2 )3—C≡C—CH2
005 (CH3)2CH— CH3—CH2 CH3—(CH2 )3—C≡C—CH2
006 Cl—CH2—CH2—CH2 CH3—CH2 CH3—(CH2 )3—C≡C—CH2
007 CH3 (CH3)2CH— CH3—(CH2 )3—C≡C—CH2
008 CH3—CH2 (CH3)2CH— CH3—(CH2 )3—C≡C—CH2
009 (CH3)2N— (CH3)2CH— CH3—(CH2 )3—C≡C—CH2
010 CH3—CH2—CH2 (CH3)2CH— CH3—(CH2 )3—C≡C—CH2
011 (CH3)2CH— (CH3)2CH— CH3—(CH2 )3—C≡C—CH2
012 Cl—CH2—CH2—CH2 (CH3)2CH— CH3—(CH2 )3—C≡C—CH2
013 CH3 CH3—CH2—CH2 CH3—(CH2 )3—C≡C—CH2
014 CH3—CH2 CH3—CH2—CH2 CH3—(CH2 )3—C≡C—CH2
015 (CH3)2N— CH3—CH2—CH2 CH3—(CH2 )3—C≡C—CH2
016 CH3—CH2—CH2 CH3—CH2—CH2 CH3—(CH2 )3—C≡C—CH2
017 (CH3)2CH— CH3—CH2—CH2 CH3—(CH2 )3—C≡C—CH2
018 Cl—CH2—CH2—CH2 CH3—CH2—CH2 CH3—(CH2 )3—C≡C—CH2
019 CH3
Figure US06864392-20050308-C00023
CH3—(CH2 )3—C≡C—CH2
020 CH3—CH2
Figure US06864392-20050308-C00024
CH3—(CH2 )3—C≡C—CH2
021 (CH3)2N—
Figure US06864392-20050308-C00025
CH3—(CH2 )3—C≡C—CH2
022 CH3—CH2—CH2
Figure US06864392-20050308-C00026
CH3—(CH2 )3—C≡C—CH2
023 (CH3)2CH—
Figure US06864392-20050308-C00027
CH3—(CH2 )3—C≡C—CH2
024 Cl—CH2—CH2—CH2
Figure US06864392-20050308-C00028
CH3—(CH2 )3—C≡C—CH2
025 CH3 CH2═CH—CH2 CH3—(CH2 )3—C≡C—CH2
026 CH3—CH2 CH2═CH—CH2 CH3—(CH2 )3—C≡C—CH2
027 (CH3)2N— CH2═CH—CH2 CH3—(CH2 )3—C≡C—CH2
028 CH3—CH2—CH2 CH2═CH—CH2 CH3—(CH2 )3—C≡C—CH2
029 (CH3)2CH— CH2═CH—CH2 CH3—(CH2 )3—C≡C—CH2
030 Cl—CH2—CH2—CH2 CH2═CH—CH2 CH3—(CH2 )3—C≡C—CH2
031 CH3 CH═C—CH2 CH3—(CH2 )3—C≡C—CH2
032 CH3—CH2 CH═C—CH2 CH3—(CH2 )3—C≡C—CH2
033 (CH3)2N— CH═C—CH2 CH3—(CH2 )3—C≡C—CH2
034 CH3—CH2—CH2 CH═C—CH2 CH3—(CH2 )3—C≡C—CH2
035 (CH3)2CH— CH═C—CH2 CH3—(CH2 )3—C≡C—CH2
036 Cl—CH2—CH2—CH2 CH═C—CH2 CH3—(CH2 )3—C≡C—CH2
037 CH3 CH3—CH2—CH(CH3)— CH3—(CH2 )3—C≡C—CH2
038 CH3—CH2 CH3—CH2—CH(CH3)— CH3—(CH2 )3—C≡C—CH2
039 (CH3)2N— CH3—CH2—CH(CH3)— CH3—(CH2 )3—C≡C—CH2
040 CH3—CH2—CH2 CH3—CH2—CH(CH3)— CH3—(CH2 )3—C≡C—CH2
041 (CH3)2CH— CH3—CH2—CH(CH3)— CH3—(CH2 )3—C≡C—CH2
042 Cl—CH2—CH2—CH2 CH3—CH2—CH(CH3)— CH3—(CH2 )3—C≡C—CH2
045 CH3 CH3—CH2
Figure US06864392-20050308-C00029
046 CH3—CH2 CH3—CH2
Figure US06864392-20050308-C00030
047 (CH3)2N— CH3—CH2
Figure US06864392-20050308-C00031
048 CH3—CH2—CH2 CH3—CH2
Figure US06864392-20050308-C00032
049 (CH3)2CH— CH3—CH2
Figure US06864392-20050308-C00033
050 Cl—CH2—CH2—CH2 CH3—CH2
Figure US06864392-20050308-C00034
51 CH3 (CH3)2CH—
Figure US06864392-20050308-C00035
052 CH3—CH2 (CH3)2CH—
Figure US06864392-20050308-C00036
053 (CH3)2N— (CH3)2CH—
Figure US06864392-20050308-C00037
054 CH3—CH2—CH2 (CH3)2CH—
Figure US06864392-20050308-C00038
055 (CH3)2CH— (CH3)2CH—
Figure US06864392-20050308-C00039
056 Cl—CH2—CH2—CH2 (CH3)2CH—
Figure US06864392-20050308-C00040
057 CH3 CH3—CH2—CH2
Figure US06864392-20050308-C00041
058 CH3—CH2 CH3—CH2—CH2
Figure US06864392-20050308-C00042
059 (CH3)2N— CH3—CH2—CH2
Figure US06864392-20050308-C00043
060 CH3—CH2—CH2 CH3—CH2—CH2
Figure US06864392-20050308-C00044
061 (CH3)2CH— CH3—CH2—CH2
Figure US06864392-20050308-C00045
062 Cl—CH2—CH2—CH2 CH3—CH2—CH2
Figure US06864392-20050308-C00046
063 CH3
Figure US06864392-20050308-C00047
Figure US06864392-20050308-C00048
064 CH3—CH2
Figure US06864392-20050308-C00049
Figure US06864392-20050308-C00050
065 (CH3)2N—
Figure US06864392-20050308-C00051
Figure US06864392-20050308-C00052
066 CH3—CH2—CH2
Figure US06864392-20050308-C00053
Figure US06864392-20050308-C00054
067 (CH3)2CH—
Figure US06864392-20050308-C00055
Figure US06864392-20050308-C00056
068 Cl—CH2—CH2—CH2
Figure US06864392-20050308-C00057
Figure US06864392-20050308-C00058
069 CH3 CH2═CH—CH2
Figure US06864392-20050308-C00059
070 CH3—CH2 CH2═CH—CH2
Figure US06864392-20050308-C00060
071 (CH3)2N— CH2═CH═CH2
Figure US06864392-20050308-C00061
072 CH3—CH2—CH2 CH2═CH—CH2
Figure US06864392-20050308-C00062
073 (CH3)2CH— CH2═CH—CH2
Figure US06864392-20050308-C00063
074 Cl—CH2—CH2—CH2 CH2═CH—CH2
Figure US06864392-20050308-C00064
075 CH3 CH═C—CH2
Figure US06864392-20050308-C00065
076 CH3—CH2 CH≡C—CH2
Figure US06864392-20050308-C00066
077 (CH3)2N— CH≡C—CH2
Figure US06864392-20050308-C00067
078 CH3—CH2—CH2 CH≡C—CH2
Figure US06864392-20050308-C00068
079 (CH3)2CH— CH≡C—CH2
Figure US06864392-20050308-C00069
080 Cl—CH2—CH2—CH2 CH≡C—CH2
Figure US06864392-20050308-C00070
081 CH3 CH3—CH2—CH(CH3)—
Figure US06864392-20050308-C00071
082 CH3—CH2 CH3—CH2—CH(CH3)—
Figure US06864392-20050308-C00072
083 (CH3)2N— CH3—CH2—CH(CH3)—
Figure US06864392-20050308-C00073
084 CH3—CH2—CH2 CH3—CH2—CH(CH3)—
Figure US06864392-20050308-C00074
085 (CH3)2CH— CH3—CH2—CH(CH3)—
Figure US06864392-20050308-C00075
086 Cl—CH2—CH2—CH2 CH3—CH2—CH(CH3)—
Figure US06864392-20050308-C00076
087 CH3 CH3—CH2 Ph—C≡C—CH2
088 CH3—CH2 CH3—CH2 Ph—C≡C—CH2
089 (CH3)2N— CH3—CH2 Ph—C≡C—CH2
090 CH3—CH2—CH2 CH3—CH2 Ph—C≡C—CH2
091 (CH3)2CH— CH3—CH2 Ph—C≡C—CH2
092 Cl—CH2—CH2—CH2 CH3—CH2 Ph—C≡C—CH2
093 CH3 (CH3)2CH— Ph—C≡C—CH2
094 CH3—CH2 (CH3)2CH— Ph—C≡C—CH2
095 (CH3)2N— (CH3)2CH— Ph—C≡C—CH2
096 CH3—CH2—CH2 (CH3)2CH— Ph—C≡C—CH2
097 (CH3)2CH— (CH3)2CH— Ph—C≡C—CH2
098 Cl—CH2—CH2—CH2 (CH3)2CH— Ph—C≡C—CH2
099 CH3 CH3—CH2—CH2 Ph—C≡C—CH2
100 CH3—CH2 CH3—CH2—CH2 Ph—C≡C—CH2
101 (CH3)2N— CH3—CH2—CH2 Ph—C≡C—CH2
102 CH3—CH2—CH2 CH3—CH2—CH2 Ph—C≡C—CH2
103 (CH3)2CH— CH3—CH2—CH2 Ph—C≡C—CH2
104 Cl—CH2—CH2—CH2 CH3—CH2—CH2 Ph—C≡C—CH2
105 CH3
Figure US06864392-20050308-C00077
Ph—C≡C—CH2
106 CH3—CH2
Figure US06864392-20050308-C00078
Ph—C≡C—CH2
107 (CH3)2N—
Figure US06864392-20050308-C00079
Ph—C≡C—CH2
108 CH3—CH2—CH2
Figure US06864392-20050308-C00080
Ph—C≡C—CH2
109 (CH3)2CH—
Figure US06864392-20050308-C00081
Ph—C≡C—CH2
110 Cl—CH2—CH2—CH2
Figure US06864392-20050308-C00082
Ph—C≡C—CH2
111 CH3 CH2═CH—CH2 Ph—C≡C—CH2
112 CH3—CH2 CH2═CH—CH2 Ph—C≡C—CH2
113 (CH3)2N— CH2═CH—CH2 Ph—C≡C—CH2
114 CH3—CH2—CH2 CH2═CH—CH2 Ph—C≡C—CH2
115 (CH3)2CH— CH2═CH—CH2 Ph—C≡C—CH2
116 Cl—CH2—CH2—CH2 CH2═CH—CH2 Ph—C≡C—CH2
117 CH3 CH≡C—CH2 Ph—C≡C—CH2
118 CH3—CH2 CH≡C—CH2 Ph—C≡C—CH2
119 (CH3)2N— CH≡C—CH2 Ph—C≡C—CH2
120 CH3—CH2—CH2 CH≡C—CH2 Ph—C≡C—CH2
121 (CH3)2CH— CH≡C—CH2 Ph—C≡C—CH2
122 Cl—CH2—CH2—CH2 CH≡C—CH2 Ph—C≡C—CH2
123 CH3 CH3—CH2—CH(CH3)— Ph—C≡C—CH2
124 CH3—CH2 CH3—CH2—CH(CH3)— Ph—C≡C—CH2
125 (CH3)2N— CH3—CH2—CH(CH3)— Ph—C≡C—CH2
126 CH3—CH2—CH2 CH3—CH2—CH(CH3)— Ph—C≡C—CH2
127 (CH3)2CH— CH3—CH2—CH(CH3)— Ph—C≡C—CH2
128 Cl—CH2—CH2—CH2 CH3—CH2—CH(CH3)— Ph—C≡C—CH2
129 CH3 CH3—CH2 (4—F—Ph)—C≡C—CH2
130 CH3—CH2 CH3—CH2 (4-F—Ph)—C≡C—CH2
131 (CH3)2N— CH3—CH2 (4-F—Ph)—C≡C—CH2
132 CH3—CH2—CH2 CH3—CH2 (4-F—Ph)—C≡C—CH2
133 (CH3)2CH— CH3—CH2 (4-F—Ph)—C≡C—CH2
134 Cl—CH2—CH2—CH2 CH3—CH2 (4-F—Ph)—C≡C—CH2
135 CH3 (CH3)2CH2 (4-F—Ph)—C≡C—CH2
136 CH3—CH2 (CH3)2CH2 (4-F—Ph)—C≡C—CH2
137 (CH3)2N— (CH3)2CH2 (4-F—Ph)—C≡C—CH2
138 CH3—CH2—CH2 (CH3)2CH2 (4-F—Ph)—C≡C—CH2
139 (CH3)2CH— (CH3)2CH2 (4-F—Ph)—C≡C—CH2
140 Cl—CH2—CH2—CH2 (CH3)2CH2 (4-F—Ph)—C≡C—CH2
141 CH3 CH3—CH2—CH2 (4-F—Ph)—C≡C—CH2
142 CH3—CH2 CH3—CH2—CH2 (4-F—Ph)—C≡C—CH2
143 (CH3)2N— CH3—CH2—CH2 (4-F—Ph)—C≡C—CH2
144 CH3—CH2—CH2 CH3—CH2—CH2 (4-F—Ph)—C≡C—CH2
145 (CH3)2CH— CH3—CH2—CH2 (4-F—Ph)—C≡C—CH2
146 Cl—CH2—CH2—CH2 CH3—CH2—CH2 (4-F—Ph)—C≡C—CH2
147 CH3
Figure US06864392-20050308-C00083
(4-F—Ph)—C≡C—CH2
148 CH3—CH2
Figure US06864392-20050308-C00084
(4-F—Ph)—C≡C—CH2
149 (CH3)2N—
Figure US06864392-20050308-C00085
(4-F—Ph)—C≡C—CH2
150 CH3—CH2—CH2
Figure US06864392-20050308-C00086
(4-F—Ph)—C≡C—CH2
151 (CH3)2CH—
Figure US06864392-20050308-C00087
(4-F—Ph)—C≡C—CH2
152 Cl—CH2—CH2—CH2
Figure US06864392-20050308-C00088
(4-F—Ph)—C≡C—CH2
153 CH3 CH2═CH—CH2 (4-F—Ph)—C≡C—CH2
154 CH3—CH2 CH2═CH—CH2 (4-F—Ph)—C≡C—CH2
155 (CH3)2N— CH2═CH—CH2 (4-F—Ph)—C≡C—CH2
156 CH3—CH2—CH2 CH2═CH—CH2 (4-F—Ph)—C≡C—CH2
157 (CH3)2CH— CH2═CH—CH2 (4-F—Ph)—C≡C—CH2
158 Cl—CH2—CH2—CH2 CH2═CH—CH2 (4-F—Ph)—C≡C—CH2
159 CH3 CH≡C—CH2 (4-F—Ph)—C≡C—CH2
160 CH3—CH2 CH≡C—CH2 (4-F—Ph)—C≡C—CH2
161 (CH3)2N— CH≡C—CH2 (4-F—Ph)—C≡C—CH2
162 CH3—CH2—CH2 CH≡C—CH2 (4-F—Ph)—C≡C—CH2
163 (CH3)2CH— CH≡C—CH2 (4-F—Ph)—C≡C—CH2
164 Cl—CH2—CH2—CH2 CH≡C—CH2 (4-F—Ph)—C≡C—CH2
165 CH3 CH3—CH2—CH(CH3)— (4-F—Ph)—C≡C—CH2
166 CH3—CH2 CH3—CH2—CH(CH3)— (4-F—Ph)—C≡C—CH2
167 (CH3)2N— CH3—CH2—CH(CH3)— (4-F—Ph)—C≡C—CH2
168 CH3—CH2—CH2 CH3—CH2—CH(CH3)— (4-F—Ph)—C≡C—CH2
169 (CH3)2CH— CH3—CH2—CH(CH3)— (4-F—Ph)—C≡C—CH2
170 Cl—CH2—CH2—CH2 CH3—CH2—CH(CH3)— (4-F—Ph)—C≡C—CH2
171 CH3 CH3—CH2 (4-Cl—Ph)—C≡C—CH2
172 CH3—CH2 CH3—CH2 (4-Cl—Ph)—C≡C—CH2
173 (CH3)2N— CH3—CH2 (4-Cl—Ph)—C≡C—CH2
174 CH3—CH2—CH2 CH3—CH2 (4-Cl—Ph)—C≡C—CH2
175 (CH3)2CH— CH3—CH2 (4-Cl—Ph)—C≡C—CH2
176 Cl—CH2—CH2—CH2 CH3—CH2 (4-Cl—Ph)—C≡C—CH2
177 CH3 (CH3)2CH— (4-Cl—Ph)—C≡C—CH2
178 CH3—CH2 (CH3)2CH— (4-Cl—Ph)—C≡C—CH2
179 (CH3)2N— (CH3)2CH— (4-Cl—Ph)—C≡C—CH2
180 CH3—CH2—CH2 (CH3)2CH— (4-Cl—Ph)—C≡C—CH2
181 (CH3)2CH— (CH3)2CH— (4-Cl—Ph)—C≡C—CH2
182 Cl—CH2—CH2—CH2 (CH3)2CH— (4-Cl—Ph)—C≡C—CH2
183 CH3 CH3—CH2—CH2 (4-Cl—Ph)—C≡C—CH2
184 CH3—CH2 CH3—CH2—CH2 (4-Cl—Ph)—C≡C—CH2
185 (CH3)2N— CH3—CH2—CH2 (4-Cl—Ph)—C≡C—CH2
186 CH3—CH2—CH2 CH3—CH2—CH2 (4-Cl—Ph)—C≡C—CH2
187 (CH3)2CH— CH3—CH2—CH2 (4-Cl—Ph)—C≡C—CH2
188 Cl—CH2—CH2—CH2 CH3—CH2—CH2 (4-Cl—Ph)—C≡C—CH2
189 CH3
Figure US06864392-20050308-C00089
(4-Cl—Ph)—C≡C—CH2
190 CH3—CH2
Figure US06864392-20050308-C00090
(4-Cl—Ph)—C≡C—CH2
191 (CH3)2N—
Figure US06864392-20050308-C00091
(4-Cl—Ph)—C≡C—CH2
192 CH3—CH2—CH2
Figure US06864392-20050308-C00092
(4-Cl—Ph)—C≡C—CH2
193 (CH3)2CH—
Figure US06864392-20050308-C00093
(4-Cl—Ph)—C≡C—CH2
194 Cl—CH2—CH2—CH2
Figure US06864392-20050308-C00094
(4-Cl—Ph)—C≡C—CH2
195 CH3 CH2═CH—CH2 (4-Cl—Ph)—C≡C—CH2
196 CH3—CH2 CH2═CH—CH2 (4-Cl—Ph)—C≡C—CH2
197 (CH3)2N— CH2═CH—CH2 (4-Cl—Ph)—C≡C—CH2
198 CH3—CH2—CH2 CH2═CH—CH2 (4-Cl—Ph)—C≡C—CH2
199 (CH3)2CH— CH2═CH—CH2 (4-Cl—Ph)—C≡C—CH2
200 Cl—CH2—CH2—CH2 CH2═CH—CH2 (4-Cl—Ph)—C≡C—CH2
201 CH3 CH≡C—CH2 (4-Cl—Ph)—C≡C—CH2
202 CH3—CH2 CH≡C—CH2 (4-Cl—Ph)—C≡C—CH2
203 (CH3)2N— CH≡C—CH2 (4-Cl—Ph)—C≡C—CH2
204 CH3—CH2—CH2 CH≡C—CH2 (4-Cl—Ph)—C≡C—CH2
205 (CH3)2CH— CH≡C—CH2 (4-Cl—Ph)—C≡C—CH2
206 Cl—CH2—CH2—CH2 CH≡C—CH2 (4-Cl—Ph)—C≡C—CH2
207 CH3 CH3—CH2—CH(CH3)— (4-Cl—Ph)—C≡C—CH2
208 CH3—CH2 CH3—CH2—CH(CH3)— (4-Cl—Ph)—C≡C—CH2
209 (CH3)2N— CH3—CH2—CH(CH3)— (4-Cl—Ph)—C≡C—CH2
210 CH3—CH2—CH2 CH3—CH2—CH(CH3)— (4-Cl—Ph)—C≡C—CH2
211 (CH3)2CH— CH3—CH2—CH(CH3)— (4-Cl—Ph)—C≡C—CH2
212 Cl—CH2—CH2—CH2 CH3—CH2—CH(CH3)— (4-Cl—Ph)—C≡C—CH2
213 CH3 CH3—CH2 (4-Br—Ph)—C≡C—CH2
214 CH3—CH2 CH3—CH2 (4-Br—Ph)—C≡C—CH2
215 (CH3)2N— CH3—CH2 (4-Br—Ph)—C≡C—CH2
216 CH3—CH2—CH2 CH3—CH2 (4-Br—Ph)—C≡C—CH2
217 (CH3)2CH— CH3—CH2 (4-Br—Ph)—C≡C—CH2
218 Cl—CH2—CH2—CH2 CH3—CH2 (4-Br—Ph)—C≡C—CH2
219 CH3 (CH3)2CH— (4-Br—Ph)—C≡C—CH2
220 CH3—CH2 (CH3)2CH— (4-Br—Ph)—C≡C—CH2
221 (CH3)2N— (CH3)2CH— (4-Br—Ph)—C≡C—CH2
222 CH3—CH2—CH2 (CH3)2CH— (4-Br—Ph)—C≡C—CH2
223 (CH3)2CH— (CH3)2CH— (4-Br—Ph)—C≡C—CH2
224 Cl—CH2—CH2—CH2 (CH3)2CH— (4-Br—Ph)—C≡C—CH2
225 CH3 CH3—CH2—CH2 (4-Br—Ph)—C≡C—CH2
226 CH3—CH2 CH3—CH2—CH2 (4-Br—Ph)—C≡C—CH2
227 (CH3)2N— CH3—CH2—CH2 (4-Br—Ph)—C≡C—CH2
228 CH3—CH2—CH2 CH3—CH2—CH2 (4-Br—Ph)—C≡C—CH2
229 (CH3)2CH— CH3—CH2—CH2 (4-Br—Ph)—C≡C—CH2
230 Cl—CH2—CH2—CH2 CH3—CH2—CH2 (4-Br—Ph)—C≡C—CH2
231 CH3
Figure US06864392-20050308-C00095
(4-Br—Ph)—C≡C—CH2
232 CH3—CH2
Figure US06864392-20050308-C00096
(4-Br—Ph)—C≡C—CH2
233 (CH3)2N—
Figure US06864392-20050308-C00097
(4-Br—Ph)—C≡C—CH2
234 CH3—CH2—CH2
Figure US06864392-20050308-C00098
(4-Br—Ph)—C≡C—CH2
235 (CH3)2CH—
Figure US06864392-20050308-C00099
(4-Br—Ph)—C≡C—CH2
236 Cl—CH2—CH2—CH2
Figure US06864392-20050308-C00100
(4-Br—Ph)—C≡C—CH2
237 CH3 CH2═CH—CH2 (4-Br—Ph)—C≡C—CH2
238 CH3—CH2 CH2═CH—CH2 (4-Br—Ph)—C≡C—CH2
239 (CH3)2N— CH2═CH—CH2 (4-Br—Ph)—C≡C—CH2
240 CH3—CH2—CH2 CH2═CH—CH2 (4-Br—Ph)—C≡C—CH2
241 (CH3)2CH— CH2═CH—CH2 (4-Br—Ph)—C≡C—CH2
242 Cl—CH2—CH2—CH2 CH2═CH—CH2 (4-Br—Ph)—C≡C—CH2
243 CH3 CH≡C—CH2 (4-Br—Ph)—C≡C—CH2
244 CH3—CH2 CH≡C—CH2 (4-Br—Ph)—C≡C—CH2
245 (CH3)2N— CH≡C—CH2 (4-Br—Ph)—C≡C—CH2
246 CH3—CH2—CH2 CH≡C—CH2 (4-Br—Ph)—C≡C—CH2
247 (CH3)2CH— CH≡C—CH2 (4-Br—Ph)—C≡C—CH2
248 Cl—CH2—CH2—CH2 CH≡C—CH2 (4-Br—Ph)—C≡C—CH2
249 CH3 CH3—CH2—CH(CH3)— (4-Br—Ph)—C≡C—CH2
250 CH3—CH2 CH3—CH2—CH(CH3)— (4-Br—Ph)—C≡C—CH2
251 (CH3)2N— CH3—CH2—CH(CH3)— (4-Br—Ph)—C≡C—CH2
252 CH3—CH2—CH2 CH3—CH2—CH(CH3)— (4-Br—Ph)—C≡C—CH2
253 (CH3)2CH— CH3—CH2—CH(CH3)— (4-Br—Ph)—C≡C—CH2
254 Cl—CH2—CH2—CH2 CH3—CH2—CH(CH3)— (4-Br—Ph)—C≡C—CH2
255 CH3 CH3—CH2 H
256 CH3—CH2 CH3—CH2 H
257 (CH3)2N— CH3—CH2 H
258 CH3—CH2—CH2 CH3—CH2 H
259 (CH3)2CH— CH3—CH2 H
260 Cl—CH2—CH2—CH2 CH3—CH2 H
261 CH3 (CH3)2CH— H
262 CH3—CH2 (CH3)2CH— H
263 (CH3)2N— (CH3)2CH— H
264 CH3—CH2—CH2 (CH3)2CH— H
265 (CH3)2CH— (CH3)2CH— H
266 Cl—CH2—CH2—CH2 (CH3)2CH— H
267 CH3 CH3—CH2—CH2 H
268 CH3—CH2 CH3—CH2—CH2 H
269 (CH3)2N— CH3—CH2—CH2 H
270 CH3—CH2—CH2 CH3—CH2—CH2 H
271 (CH3)2CH— CH3—CH2—CH2 H
272 Cl—CH2—CH2—CH2 CH3—CH2—CH2 H
273 CH3
Figure US06864392-20050308-C00101
H
274 CH3—CH2
Figure US06864392-20050308-C00102
H
275 (CH3)2N—
Figure US06864392-20050308-C00103
H
276 CH3—CH2—CH2
Figure US06864392-20050308-C00104
H
277 (CH3)2CH—
Figure US06864392-20050308-C00105
H
278 Cl—CH2—CH2—CH2
Figure US06864392-20050308-C00106
H
279 CH3 CH2═CH—CH2 H
280 CH3—CH2 CH2═CH—CH2 H
281 (CH3)2N— CH2═CH—CH2 H
282 CH3—CH2—CH2 CH2═CH—CH2 H
283 (CH3)2CH— CH2═CH—CH2 H
284 Cl—CH2—CH2—CH2 CH2═CH—CH2 H
285 CH3 CH≡C—CH2 H
286 CH3—CH2 CH≡C—CH2 H
287 (CH3)2N— CH≡C—CH2 H
288 CH3—CH2—CH2 CH≡C—CH2 H
289 (CH3)2CH— CH≡C—CH2 H
290 Cl—CH2—CH2—CH2 CH≡C—CH2 H
291 CH3 CH3—CH2—CH(CH3)— H
292 CH3—CH2 CH3—CH2—CH(CH3)— H
293 (CH3)2N— CH3—CH2—CH(CH3)— H
294 CH3—CH2—CH2 CH3—CH2—CH(CH3)— H
295 (CH3)2CH— CH3—CH2—CH(CH3)— H
296 Cl—CH2—CH2—CH2 CH3—CH2—CH(CH3)— H
297 CH3 CH3—CH2 Ph—CH2
298 CH3—CH2 CH3—CH2 Ph—CH2
299 (CH3)2N— CH3—CH2 Ph—CH2
300 CH3—CH2—CH2 CH3—CH2 Ph—CH2
301 (CH3)2CH— CH3—CH2 Ph—CH2
302 Cl—CH2—CH2—CH2 CH3—CH2 Ph—CH2
303 CH3 (CH3)2CH— Ph—CH2
304 CH3—CH2 (CH3)2CH— Ph—CH2
305 (CH3)2N— (CH3)2CH— Ph—CH2
306 CH3—CH2—CH2 (CH3)2CH— Ph—CH2
307 (CH3)2CH— (CH3)2CH— Ph—CH2
308 Cl—CH2—CH2—CH2 (CH3)2CH— Ph—CH2
309 CH3 CH3—CH2—CH2 Ph—CH2
310 CH3—CH2 CH3—CH2—CH2 Ph—CH2
311 (CH3)2N— CH3—CH2—CH2 Ph—CH2
312 CH3—CH2—CH2 CH3—CH2—CH2 Ph—CH2
313 (CH3)2CH— CH3—CH2—CH2 Ph—CH2
314 Cl—CH2—CH2—CH2 CH3—CH2—CH2 Ph—CH2
315 CH3
Figure US06864392-20050308-C00107
Ph—CH2
316 CH3—CH2
Figure US06864392-20050308-C00108
Ph—CH2
317 (CH3)2N—
Figure US06864392-20050308-C00109
Ph—CH2
318 CH3—CH2—CH2
Figure US06864392-20050308-C00110
Ph—CH2
319 (CH3)2CH—
Figure US06864392-20050308-C00111
Ph—CH2
320 Cl—CH2—CH2—CH2
Figure US06864392-20050308-C00112
Ph—CH2
321 CH3 CH2═CH—CH2 Ph—CH2
322 CH3—CH2 CH2═CH—CH2 Ph—CH2
323 (CH3)2N— CH2═CH—CH2 Ph—CH2
324 CH3—CH2—CH2 CH2═CH—CH2 Ph—CH2
325 (CH3)2CH— CH2═CH—CH2 Ph—CH2
326 Cl—CH2—CH2—CH2 CH2═CH—CH2 Ph—CH2
327 CH3 CH≡C—CH2 Ph—CH2
328 CH3—CH2 CH≡C—CH2 Ph—CH2
329 (CH3)2N— CH≡C—CH2 Ph—CH2
330 CH3—CH2—CH2 CH≡C—CH2 Ph—CH2
331 (CH3)2CH— CH≡C—CH2 Ph—CH2
332 Cl—CH2—CH2—CH2 CH≡C—CH2 Ph—CH2
333 CH3 CH3—CH2—CH(CH3)— Ph—CH2
334 CH3—CH2 CH3—CH2—CH(CH3)— Ph—CH2
335 (CH3)2N— CH3—CH2—CH(CH3)— Ph—CH2
336 CH3—CH2—CH2 CH3—CH2—CH(CH3)— Ph—CH2
337 (CH3)2CH— CH3—CH2—CH(CH3)— Ph—CH2
338 Cl—CH2—CH2—CH2 CH3—CH2—CH(CH3)— Ph—CH2
339 CH3 CH3—CH2 (4-Cl—Ph)—CH2
340 CH3—CH2 CH3—CH2 (4-Cl—Ph)—CH2
341 (CH3)2N— CH3—CH2 (4-Cl—Ph)—CH2
342 CH3—CH2—CH2 CH3—CH2 (4-Cl—Ph)—CH2
343 (CH3)2CH— CH3—CH2 (4-Cl—Ph)—CH2
344 Cl—CH2—CH2—CH2 CH3—CH2 (4-Cl—Ph)—CH2
345 CH3 (CH3)2CH— (4-Cl—Ph)—CH2
346 CH3—CH2 (CH3)2CH— (4-Cl—Ph)—CH2
347 (CH3)2N— (CH3)2CH— (4-Cl—Ph)—CH2
348 CH3—CH2—CH2 (CH3)2CH— (4-Cl—Ph)—CH2
349 (CH3)2CH— (CH3)2CH— (4-Cl—Ph)—CH2
350 Cl—CH2—CH2—CH2 (CH3)2CH— (4-Cl—Ph)—CH2
351 CH3 CH3—CH2—CH2 (4-Cl—Ph)—CH2
352 CH3—CH2 CH3—CH2—CH2 (4-Cl—Ph)—CH2
353 (CH3)2N— CH3—CH2—CH2 (4-Cl—Ph)—CH2
354 CH3—CH2—CH2 CH3—CH2—CH2 (4-Cl—Ph)—CH2
355 (CH3)2CH— CH3—CH2—CH2 (4-Cl—Ph)—CH2
356 Cl—CH2—CH2—CH2 CH3—CH2—CH2 (4-Cl—Ph)—CH2
357 CH3
Figure US06864392-20050308-C00113
(4-Cl—Ph)—CH2
358 CH3—CH2
Figure US06864392-20050308-C00114
(4-Cl—Ph)—CH2
359 (CH3)2N—
Figure US06864392-20050308-C00115
(4-Cl—Ph)—CH2
360 CH3—CH2—CH2
Figure US06864392-20050308-C00116
(4-Cl—Ph)—CH2
361 (CH3)2CH—
Figure US06864392-20050308-C00117
(4-Cl—Ph)—CH2
362 Cl—CH2—CH2—CH2
Figure US06864392-20050308-C00118
(4-Cl—Ph)—CH2
363 CH3 CH2═CH—CH2 (4-Cl—Ph)—CH2
364 CH3—CH2 CH2═CH—CH2 (4-Cl—Ph)—CH2
365 (CH3)2N— CH2═CH—CH2 (4-Cl—Ph)—CH2
366 CH3—CH2—CH2 CH2═CH—CH2 (4-Cl—Ph)—CH2
367 (CH3)2CH— CH2═CH—CH2 (4-Cl—Ph)—CH2
368 Cl—CH2—CH2—CH2 CH2═CH—CH2 (4-Cl—Ph)—CH2
369 CH3 CH≡C—CH2 (4-Cl—Ph)—CH2
370 CH3—CH2 CH≡C—CH2 (4-Cl—Ph)—CH2
371 (CH3)2N— CH≡C—CH2 (4-Cl—Ph)—CH2
372 CH3—CH2—CH2 CH≡C—CH2 (4-Cl—Ph)—CH2
373 (CH3)2CH— CH≡C—CH2 (4-Cl—Ph)—CH2
374 Cl—CH2—CH2—CH2 CH≡C—CH2 (4-Cl—Ph)—CH2
375 CH3 CH3—CH2—CH(CH3)— (4-Cl—Ph)—CH2
376 CH3—CH2 CH3—CH2—CH(CH3)— (4-Cl—Ph)—CH2
378 (CH3)2N— CH3—CH2—CH(CH3)— (4-Cl—Ph)—CH2
379 CH3—CH2—CH2 CH3—CH2—CH(CH3)— (4-Cl—Ph)—CH2
380 (CH3)2CH— CH3—CH2—CH(CH3)— (4-Cl—Ph)—CH2
381 Cl—CH2—CH2—CH2 CH3—CH2—CH(CH3)— (4-Cl—Ph)—CH2
382 CH3 CH3—CH2 (3-Cl—Ph)—CH2
383 CH3—CH2 CH3—CH2 (3-Cl—Ph)—CH2
384 (CH3)2N— CH3—CH2 (3-Cl—Ph)—CH2
385 CH3—CH2—CH2 CH3—CH2 (3-Cl—Ph)—CH2
386 (CH3)2CH— CH3—CH2 (3-Cl—Ph)—CH2
387 Cl—CH2—CH2—CH2 CH3—CH2 (3-Cl—Ph)—CH2
388 CH3 (CH3)2CH— (3-Cl—Ph)—CH2
389 CH3—CH2 (CH3)2CH— (3-Cl—Ph)—CH2
390 (CH3)2N— (CH3)2CH— (3-Cl—Ph)—CH2
391 CH3—CH2—CH2 (CH3)2CH— (3-Cl—Ph)—CH2
392 (CH3)2CH— (CH3)2CH— (3-Cl—Ph)—CH2
393 Cl—CH2—CH2—CH2 (CH3)2CH— (3-Cl—Ph)—CH2
394 CH3 CH3—CH2—CH2 (3-Cl—Ph)—CH2
395 CH3—CH2 CH3—CH2—CH2 (3-Cl—Ph)—CH2
396 (CH3)2N— CH3—CH2—CH2 (3-Cl—Ph)—CH2
397 CH3—CH2—CH2 CH3—CH2—CH2 (3-Cl—Ph)—CH2
398 (CH3)2CH— CH3—CH2—CH2 (3-Cl—Ph)—CH2
399 Cl—CH2—CH2—CH2 CH3—CH2—CH2 (3-Cl—Ph)—CH2
400 CH3
Figure US06864392-20050308-C00119
(3-Cl—Ph)—CH2
401 CH3—CH2
Figure US06864392-20050308-C00120
(3-Cl—Ph)—CH2
402 (CH3)2N—
Figure US06864392-20050308-C00121
(3-Cl—Ph)—CH2
403 CH3—CH2—CH2
Figure US06864392-20050308-C00122
(3-Cl—Ph)—CH2
404 (CH3)2CH—
Figure US06864392-20050308-C00123
(3-Cl—Ph)—CH2
405 Cl—CH2—CH2—CH2
Figure US06864392-20050308-C00124
(3-Cl—Ph)—CH2
406 CH3 CH2═CH—CH2 (3-Cl—Ph)—CH2
407 CH3—CH2 CH2═CH—CH2 (3-Cl—Ph)—CH2
408 (CH3)2N— CH2═CH—CH2 (3-Cl—Ph)—CH2
409 CH3—CH2—CH2 CH2═CH—CH2 (3-Cl—Ph)—CH2
410 (CH3)2CH— CH2═CH—CH2 (3-Cl—Ph)—CH2
411 Cl—CH2—CH2—CH2 CH2═CH—CH2 (3-Cl—Ph)—CH2
412 CH3 CH≡C—CH2 (3-Cl—Ph)—CH2
413 CH3—CH2 CH≡C—CH2 (3-Cl—Ph)—CH2
414 (CH3)2N— CH≡C—CH2 (3-Cl—Ph)—CH2
415 CH3—CH2—CH2 CH≡C—CH2 (3-Cl—Ph)—CH2
416 (CH3)2CH— CH≡C—CH2 (3-Cl—Ph)—CH2
417 Cl—CH2—CH2—CH2 CH≡C—CH2 (3-Cl—Ph)—CH2
418 CH3 CH3—CH2—CH(CH3)— (3-Cl—Ph)—CH2
419 CH3—CH2 CH3—CH2—CH(CH3)— (3-Cl—Ph)—CH2
420 (CH3)2N— CH3—CH2—CH(CH3)— (3-Cl—Ph)—CH2
421 CH3—CH2—CH2 CH3—CH2—CH(CH3)— CH(CH3)—(3-Cl—Ph)—CH2
422 (CH3)2CH— CH3—CH2—CH(CH3)— (3-Cl—Ph)—CH2
423 Cl—CH2—CH2—CH2 CH3—CH2—CH(CH3)— (3-Cl—Ph)—CH2
424 CH3 CH3—CH2 (3-CF3—Ph)—CH2
425 CH3—CH2 CH3—CH2 (3-CF3—Ph)—CH2
426 (CH3)2N— CH3—CH2 (3-CF3—Ph)—CH2
427 CH3—CH2—CH2 CH3—CH2 (3-CF3—Ph)—CH2
428 (CH3)2CH— CH3—CH2 (3-CF3—Ph)—CH2
429 Cl—CH2—CH2—CH2 CH3—CH2 (3-CF3—Ph)—CH2
430 CH3 (CH3)2CH— (3-CF3—Ph)—CH2
431 CH3—CH2 (CH3)2CH— (3-CF3—Ph)—CH2
432 (CH3)2N— (CH3)2CH— (3-CF3—Ph)—CH2
433 CH3—CH2—CH2 (CH3)2CH— (3-CF3—Ph)—CH2
434 (CH3)2CH— (CH3)2CH— (3-CF3—Ph)—CH2
435 Cl—CH2—CH2—CH2 (CH3)2CH— (3-CF3—Ph)-CH2
436 CH3 CH3—CH2—CH2 (3-CF3—Ph)—CH2
437 CH3—CH2 CH3—CH2—CH2 (3-CF3—Ph)—CH2
438 (CH3)2N— CH3—CH2—CH2 (3-CF3—Ph)—CH2
439 CH3—CH2—CH2 CH3—CH2—CH2 (3-CF3—Ph)—CH2
440 (CH3)2CH— CH3—CH2—CH2 (3-CF3—Ph)—CH2
441 Cl—CH2—CH2—CH2 CH3—CH2—CH2 (3-CF3—Ph)—CH2
442 CH3
Figure US06864392-20050308-C00125
(3-CF3—Ph)—CH2
443 CH3—CH2
Figure US06864392-20050308-C00126
(3-CF3—Ph)—CH2
444 (CH3)2N—
Figure US06864392-20050308-C00127
(3-CF3—Ph)—CH2
445 CH3—CH2—CH2
Figure US06864392-20050308-C00128
(3-CF3—Ph)—CH2
446 (CH3)2CH—
Figure US06864392-20050308-C00129
(3-CF3—Ph)—CH2
447 Cl—CH2—CH2—CH2
Figure US06864392-20050308-C00130
(3-CF3—Ph)—CH2
448 CH3 CH2═CH—CH2 (3-CF3—Ph)—CH2
449 CH3—CH2 CH2═CH—CH2 (3-CF3—Ph)—CH2
450 (CH3)2N— CH2═CH—CH2 (3-CF3—Ph)—CH2
451 CH3—CH2—CH2 CH2═CH—CH2 (3-CF3—Ph)—CH2
452 (CH3)2CH— CH2═CH—CH2 (3-CF3—Ph)—CH2
453 Cl—CH2—CH2—CH2 CH2═CH—CH2 (3-CF3—Ph)—CH2
454 CH3 CH≡C—CH2 (3-CF3—Ph)—CH2
455 CH3—CH2 CH≡C—CH2 (3-CF3—Ph)—CH2
456 (CH3)2N— CH≡C—CH2 (3-CF3—Ph)—CH2
457 CH3—CH2—CH2 CH≡C—CH2 (3-CF3—Ph)—CH2
458 (CH3)2CH— CH≡C—CH2 (3-CF3—Ph)—CH2
459 Cl—CH2—CH2—CH2 CH═C—CH2 (3-CF3—Ph)—CH2
460 CH3 CH3—CH2—CH(CH3)— (3-CF3—Ph)—CH2
461 CH3—CH2 CH3—CH2—CH(CH3)— (3-CF3—Ph)—CH2
462 (CH3)2N— CH3—CH2—CH(CH3)— (3-CF3—Ph)—CH2
463 CH3—CH2—CH2 CH3—CH2—CH(CH3)— (3-CF3—Ph)—CH2
464 (CH3)2CH— CH3—CH2—CH(CH3)— (3-CF3—Ph)—CH2
465 Cl—CH2—CH2—CH2 CH3—CH2—CH(CH3)— (3-CF3—Ph)—CH2
TABLE 7
Compounds represented by the Formula I.7 where the combination of the groups
R1, and R3 corresponds to each row in table B.
I.7
Figure US06864392-20050308-C00131
TABLE 8
Compounds represented by the Formula I.8 where the combination of
the groups R1, and R3 corresponds to each row in table B.
Figure US06864392-20050308-C00132
I.8
TABLE 9
Compounds represented by the Formula I.9 where the combination of
the groups R1, and R3 corresponds to each row in table B.
Figure US06864392-20050308-C00133
I.9
TABLE 10
Compounds represented by the Formula I.10 where the combination of
the groups R1, and R3 corresponds to each row in table B.
Figure US06864392-20050308-C00134
I.10
TABLE 11
Compounds represented by the Formula I.11 where the combination of
the groups R1, and R3 corresponds to each row in table B.
Figure US06864392-20050308-C00135
I.11
TABLE 12
Compounds represented by the Formula I.12 where the
combination of the groups R1, and R3
corresponds to each row in table B.
1.12
Figure US06864392-20050308-C00136
TABLE B
No. R1 R3
001 (CH3—CH2)2N— CH3—CH2
002 CH3—CH2—(CH3)N— CH3—CH2
003
Figure US06864392-20050308-C00137
CH3—CH2
004 CH3—(CH2)2—CH2 CH3—CH2
005 (CH3)2CH—CH2 CH3—CH2
006 CH3—CH2—(CH3)CH— CH3—CH2
007 (CH3)3C— CH3—CH2
008 CH2═CH— CH3—CH2
009
Figure US06864392-20050308-C00138
CH3—CH2
010 (CH3—CH2)2N— (CH3)2CH—
011 CH3—CH2—(CH3)N— (CH3)2CH—
012
Figure US06864392-20050308-C00139
(CH3)2CH—
013 CH3—(CH2)2—CH2 (CH3)2CH—
014 (CH3)2CH—CH2 (CH3)2CH—
015 CH3—CH2—(CH3)CH— (CH3)2CH—
016 (CH3)3C— (CH3)2CH—
017 CH2═CH— (CH3)2CH—
018
Figure US06864392-20050308-C00140
(CH3)2CH—
019 (CH3—CH2)2N— CH3—CH2—CH2
020 CH3—CH2—(CH3)N— CH3—CH2—CH2
021
Figure US06864392-20050308-C00141
CH3—CH2—CH2
022 CH3—(CH2)2—CH2 CH3—CH2—CH2
023 (CH3)2CH—CH2 CH3—CH2—CH2
024 CH3—CH2—(CH3)CH— CH3—CH2—CH2
025 (CH3)3C— CH3—CH2—CH2
026 CH2═CH— CH3—CH2—CH2
027
Figure US06864392-20050308-C00142
CH3—CH2—CH2
028 (CH3—CH2)2N— CH3—CH2—(CH3)CH—
029 CH3—CH2—(CH3)N— CH3—CH2—(CH3)CH—
030
Figure US06864392-20050308-C00143
CH3—CH2—(CH3)CH—
031 CH3—(CH2)2—CH2 CH3—CH2—(CH3)CH—
032 (CH3)2CH—CH2 CH3—CH2—(CH3)CH—
033 CH3—CH2—(CH3)CH— CH3—CH2—(CH3)CH—
034 (CH3)3C— CH3—CH2—(CH3)CH—
035 CH2═CH— CH3—CH2—(CH3)CH—
036
Figure US06864392-20050308-C00144
CH3—CH2—(CH3)CH—
037 (CH3—CH2)2N—
Figure US06864392-20050308-C00145
038 CH3—CH2—(CH3)N—
Figure US06864392-20050308-C00146
039
Figure US06864392-20050308-C00147
Figure US06864392-20050308-C00148
040 CH3(CH2)2—CH2
Figure US06864392-20050308-C00149
041 (CH3)2CH—CH2
Figure US06864392-20050308-C00150
042 CH3—CH2—(CH3)CH—
Figure US06864392-20050308-C00151
043 (CH3)3C—
Figure US06864392-20050308-C00152
044 CH2═CH—
Figure US06864392-20050308-C00153
045
Figure US06864392-20050308-C00154
Figure US06864392-20050308-C00155
046 CH3 HO—CH2
047 CH3—CH2 HO—CH2
048 (CH3)2N— HO—CH2
049 CH3—CH2—CH2 HO—CH2
050 (CH3)2CH— HO—CH2
051 CH3—CH2—(CH3)CH— HO—CH2
052 CH3 HO—(CH3)CH—
053 CH3—CH2 HO—(CH3)CH—
054 (CH3)2N— HO—(CH3)CH—
055 CH3—CH2—CH2 HO—(CH3)CH—
056 (CH3)2CH— HO—(CH3)CH—
057 CH3—CH2—(CH3)CH— HO—(CH3)CH—
058 CH3 (CH3)3C—O—(CH3)CH—
059 CH3—CH2 (CH3)3C—O—(CH3)CH—
060 (CH3)2N— (CH3)3C—O—(CH3)CH—
061 CH3—CH2—CH2 (CH3)3C—O—(CH3)CH—
062 (CH3)2CH— (CH3)3C—O—(CH3)CH—
063 CH3—CH2—(CH3)CH— (CH3)3C—O—(CH3)CH—
064 CH3 CH3—S—CH2—CH2
065 CH3—CH2 CH3—S—CH2—CH2
066 (CH3)2N— CH3—S—CH2—CH2
067 CH3—CH2—CH2 CH3—S—CH2—CH2
068 (CH3)2CH— CH3—S—CH2—CH2
069 CH3—CH2—(CH3)CH— CH3—S—CH2—CH2
070 CH3 HS—CH2—CH2
071 CH3—CH2 HS—CH2—CH2
072 (CH3)2N— HS—CH2—CH2
073 CH3—CH2—CH2 HS—CH2—CH2
074 (CH3)2CH— HS—CH2—CH2
075 CH3—CH2—(CH3)CH— HS—CH2—CH2
076 CH3 (CH3)3C—
077 CH3—CH2 (CH3)3C—
078 (CH3)2N— (CH3)3C—
079 CH3—CH2—CH2 (CH3)3C—
080 (CH3)2CH— (CH3)3C—
081 CH3—CH2—(CH3)CH— (CH3)3C—
TABLE 13
Compounds represented by the Formula I.13 where the combination of
the group R8 corresponds to each row in table C.
Figure US06864392-20050308-C00156
I.13
TABLE 14
Compounds represented by the Formula I.14 where the combination of
the group R8 corresponds to each row in table C.
Figure US06864392-20050308-C00157
I.14
TABLE 15
Compounds represented by the Formula 1.15 where the combination
of the group R8 corresponds to each row in table C.
1.15
Figure US06864392-20050308-C00158
TABLE C
No. R8
001 CH3—CH2—C(CH3)H—C≡C—CH2
002 (CH3)3C—C≡C—CH2
003 (CH3)2CH—CH2—C≡C—CH2
004 CH3—(CH2)4—C≡C—CH2
005
Figure US06864392-20050308-C00159
006
Figure US06864392-20050308-C00160
007 (4-CH3—Ph)—C≡C—CH2
008 (2-Cl—Ph)—C≡C—CH2
009 (3-Cl—Ph)—C≡C—CH2
010 (3-Br—Ph)—C≡C—CH2
011 (3-F—Ph)—C≡C—CH2
012 (3-CH3—Ph)—C≡C—CH2
013 (2,4-di-Cl—Ph)—C≡C—CH2
014 (3,4-di-Cl—Ph)—C≡C—CH2
015 (3,4-di-F—Ph)—C≡C—CH2
016 (3-CH3-4-Cl—Ph)—C≡C—CH2
017 (3-CH3-4-Br—Ph)—C≡C—CH2
018 (3-CF3—Ph)—C≡C—CH2
019 (4-CF3O—Ph)—C≡C—CH2
020 (4-Et—Ph)—C≡C—CH2
021 [4-(CH3)3C—Ph]—C≡C—CH2
022 (4-CH2═CH—Ph)—C≡C—CH2
023 (4-CH≡C—Ph)—C≡C—CH2
024 (4-CH3—CO—Ph)—C≡C—CH2
025 (4-CH3OOC—Ph)—C≡C—CH2
026 (4-CH3O—Ph)—C≡C—CH2
027
Figure US06864392-20050308-C00161
028
Figure US06864392-20050308-C00162
029
Figure US06864392-20050308-C00163
030
Figure US06864392-20050308-C00164
031 Ph—(CH3)CH—
032 Ph—(CH3)2C—
033 (3-F—Ph)—CH2
034 (4-Br—Ph)—CH2
035 (4-J—Ph)—CH2
036 (4-CH3—Ph)—CH2
037 (4-CH3O—Ph)—CH2
038 (4-CF3O—Ph)—CH2
039 (4-F—Ph)—CH2
040 (2,4-di-F—Ph)—CH2
041 (3,4-di-F—Ph)—CH2
042 (3,4-di-Br—Ph)—CH2
043 (3,4-di-Cl—Ph)—CH2
044 (3-Cl-4-CH3-Ph)—CH 2
045 (3-CH3-4-Cl—Ph)—CH2
046 (2,4,5-tri-Cl—Ph)—CH2
047
Figure US06864392-20050308-C00165
048
Figure US06864392-20050308-C00166
049
Figure US06864392-20050308-C00167
050
Figure US06864392-20050308-C00168
051
Figure US06864392-20050308-C00169
052
Figure US06864392-20050308-C00170
053
Figure US06864392-20050308-C00171
054
Figure US06864392-20050308-C00172
055
Figure US06864392-20050308-C00173
056
Figure US06864392-20050308-C00174
057 Ph—CH═CH—CH2
058 (4-Cl—Ph)—CH═CH—CH2
059 (4-F—Ph)—CH═CH—CH2
060 (4-Br—Ph)—CH═CH—CH2
061 (3-CF3—Ph)—CH═CH2
062 Ph—CH2—CH2
063 Ph—(CH2)2—CH2
064 (4-Cl—Ph)—(CH2)2—CH2
065 (4-Br—Ph)—(CH2)2—CH2
066 Ph—O—CH2—CH2
067 (4-Cl—Ph)—O—CH2—CH2
068 (4-F—Ph)—O—CH2—CH2
069 (4-Br—Ph)—O—CH2—CH2
070 (3-F—Ph)—O—CH2—CH2
071 (3,4-di-Cl—Ph)—O—CH2—CH2
072 (4-Cl—Ph)—O—(CH3)CH—CH2
073 (3,4-di-Cl—Ph)—O—(CH3)CH—CH2
074 Ph—N(CH3)—CH2—CH2
075 Ph—N(CH2—CH3)—CH2—CH2
076 Ph—S—CH2—CH2
077 (4-Cl—Ph)—S—CH2—CH2
Formulations may be prepared analogously to those described in, for example, WO 95/30651.
BIOLOGICAL EXAMPLES D-1: Action Against Plasmopara viticola (Downy Mildew) on Vines
5 week old grape seedlings cv. Gutedel are treated with the formulated test compound in a spray chamber. One day after application grape plants are inoculated by spraying a sporangia suspension (4×104 sporangia/ml) on the lower leaf side of the test plants. After an incubation period of 6 days at +21° C. and 95% r. h. in a greenhouse the disease incidence is assessed.
Compounds of Tables 1 to 15 exhibit a good fungicidal action against Plasmopara viticola on vines. Compounds A1.1, A1.2, A1.3, A1.4, A1.5 and A1.6 at 200 ppm inhibit fungal infestation in this test to a least 80%, while under the same conditions untreated control plants are infected by the phytopathogenic fungi to over 80%.
D-2: Action Against Phytophthora (Late Blight) on Tomato Plants
3 week old tomato plants cv. Roter Gnom are treated with the formulated test compound in a spray chamber. Two day after application the plants are inoculated by spraying a sporangia suspension (2×104 sporangia/mI) on the test plants. After an incubation period of 4 days at +18° C. and 95% r. h. in a growth chamber the disease incidence is assessed. Compounds of Tables 1 to 15 exhibit a long-lasting effect against fungus infestation. Compounds A1.1, A1.2, A1.3, A1.4, A1.5 and A1.6 at 200 ppm inhibit fungal infestation in this test to a least 80%, while under the same conditions untreated control plants are infected by the phytopathogenic fungi to over 80%.
D-3: Action Against Phytophthora (Late Blight) on Potato Plants
5 week old potato plants cv. Bintje are treated with the formulated test compound in a spray chamber. Two day after application the plants are inoculated by spraying a sporangia suspension (14×104 sporangia/ml) on the test plants. After an incubation period of 4 days at +18° C. and 95% r. h. in a growth chamber the disease incidence is assessed. Fungal infestation is effectively controlled with compounds of Tables 1 to 15. Compounds A1.1, A1.2, A1.3, A1.4, A1.5 and A1.6 at 200 ppm inhibit fungal infestation in this test to a least 80%, while under the same conditions untreated control plants are infected by the phytopathogenic fungi to over 80%.

Claims (15)

1. α-sulfin- and α-sulfonamino acid amides of formula I
Figure US06864392-20050308-C00175
including the optical isomers thereof and mixtures of such isomers,
wherein
n is a number zero or one;
R1 is C1-C12alkyl, C1-C12alkyl substituted with C1-C4alkoxy, C1-C4alkylthio, C1-C4alkylsulfonyl, C3-C8cycloalkyl, cyano, C1-C6alkoxycarbonyl, C3-C6alkenyloxycarbonyl or C3-C8alkynyloxycarbonyl; C3-C8cycloalkyl; C2-C12alkenyl; C2-C12alkynyl; C1-C12halogenalkyl; or a group NR9R10 wherein R9 and R10 are each independently of the other C1-C6alkyl, or together are tetra- or penta-methylene;
R2 and R3 are each independently hydrogen; C1-C8alkyl; C1-C8alkyl substituted with hydroxy, mercapto, C1-C4alkoxy or C1-C4alkylthio; C3-C8alkenyl; C3-C8alkynyl; C3-C8cycloalkyl; C3-C3cycloalkyl-C1-C4alkyl; or the two groups R2 and R3 together with the carbon atom to which they are bonded form a three- to eight-membered hydrocarbon ring;
R4, R5, R6 and R7 are each independently hydrogen or C1-C4alkyl;
Figure US06864392-20050308-C00176
R11, R12, R14, R15 and R17 are each independently hydrogen or C1-C4alkyl,
R13 is C4-C12alkyl; C1-C12halogenalkyl; C3-C8cycloalkyl; optionally substituted aryl or optionally substituted heteroaryl,
R16 is optionally substituted aryl or optionally substituted heteroaryl; and
Z is oxygen, sulfur —CR18R19— or —NR20—, wherein R18, R19 and R20 independently of each other are hydrogen or C1-C4alkyl.
2. A compound according to claim 1 wherein n is one.
3. A compound of formula I according to claim 1 wherein
R1 is C1-C12alkyl, C1-C12alkyl substituted with C1-C4alkoxy, C1-C4alkylthio, or C1-C4alkylsulfonyl; C3-C8cycloalkyl; C2-C12alkenyl; C2-C12alkynyl; C1-C12halogenalkyl; or a group NR9R10 wherein R9 and R10 are each independently of the other hydrogen or C1-C6alkyl, or together are tetra- or penta-methylene.
4. A compound of formula I according to claim 1 wherein
R2 is hydrogen and R3 is C1-C8alkyl, C1-C8alkyl, optionally substituted by hydroxy, C1-C4alkoxy, mercapto or C1-C4alkylthio; C3-C8alkenyl; C3-C8alkynyl; C3-C8cycloalkyl or C3-C8cycloalkyl-C1-C4alkyl.
5. A compound of formula I according to claim 1 wherein R4 is hydrogen, methyl or ethyl.
6. A compound of formula I according to claim 1 wherein
R5, R6 and R7 are each independently hydrogen or methyl.
7. A compound of formula I according to claim 1 wherein
R11, R12, R14, R15 and R17 are each independently hydrogen or methyl.
8. A compound of formula I according to claim 1 wherein
R13 is C4-C12alkyl; C1-C12halogenalkyl; C3-C8cycloalkyl; optionally substituted aryl or optionally substituted heteroaryl consisting of one or two condensed five or six membered rings with 1 to 4 identical or different heteroatoms selected from oxygen, nitrogen or sulfur.
9. A compound of formula I according to claim 1 wherein
R16 is optionally substituted aryl or optionally substituted heteroaryl consisting of one or two condensed five or six membered rings with 1 to 4 identical or different heteroatoms selected from oxygen, nitrogen or sulfur.
10. A compound of formula I according to claim 1 wherein Z is oxygen, sulfur or —CH2—.
11. A compound of formula I according to claim 1 wherein
n is one;
R1 is C1-C4alkyl, vinyl; C1-C4halogenalkyl; or dimethylamino;
R2 is hydrogen and R3 is isopropyl;
R4, R5, R6, R7, R11, R12, R14, R15 and R17 are each hydrogen;
R13 is C4-C8alkyl; C1-C6halogenalkyl; C3-C8cycloalkyl; phenyl, pyridyl, with each of the aromatic ring being optionally substituted by 1 to 3 substituents selected from the group consisting of C1-C8alkyl, C1-C8halogenalkyl, C1-C8alkoxy, C1-C8halogenalkoxy, C1-C8alkylthio, C1-C8halogenalkylthio, halogen, cyano, nitro and C1-C8alkoxycarbonyl;
R16 is phenyl, pyridyl, with each of the aromatic ring being optionally substituted by 1 to 3 substituents selected from the group consisting of C1-C8alkyl, C1-C8halogenalky, C1-C8alkoxy, C1-C8halogenalkoxy, C1-C8alkylthio, C1-C8halogenalkylthio, halogen, cyano, nitro and C1-C8alkoxycarbonyl; and
Z is oxygen.
12. A process for the preparation of a compound of formula I according to claim 1, which comprises reacting
a) an amino acid of formula II or a carboxy-activated derivative thereof
Figure US06864392-20050308-C00177
 wherein R1, n, R2 and R3 are as defined for formula I is reacted with an amine of formula III
Figure US06864392-20050308-C00178
 wherein R4, R5, R6, R7 and R8 are as defined for formula I optionally in the presence of a base and optionally in the presence of a diluting agent, or
b) an amino acid derivative of formula VI
Figure US06864392-20050308-C00179
 wherein R2, R3, R4, R5, R6, R7 and R8 are as defined for formula I with a sulfonyl halide or a sulfinyl halide of formula V
Figure US06864392-20050308-C00180
 wherein R1 and n are as defined for formula I and X is halide, preferentially chlorine or bromine, or
c) a phenol of formula VII
Figure US06864392-20050308-C00181
 wherein R1, n, R2, R3, R4, R5, R6 and R7 are as defined for formula I with a compound of formula VIII
Figure US06864392-20050308-C00182
 wherein R8 is as defined for formula I and Y is a leaving group like a halide such as a chloride or bromide or a sulfonic ester such as a tosylate, mesylate or triflate.
13. A process for the preparation of a compound of formula Ia
Figure US06864392-20050308-C00183
wherein R1, n, R2, R3, R4, R5, R6, R7, R11, R12 and R13 are defined in claim 1 for formula I which comprises reacting a compound of formula IX
Figure US06864392-20050308-C00184
wherein R1, n, R2, R3, R4, R5, R6, R7, R11, R12 and R13 are defined for formula I with hydrogen.
14. A composition for controlling and protecting against phytopathogenic microorganisms, comprising a compound of formula I according to claim 1 as active ingredient together with a suitable carrier.
15. A method of controlling and preventing an infestation of crop plants by phytopathogenic microorganisms, preferably fungal organisms, which comprises the application of a compound of formula I according to claim 1 as active ingredient to the plant, to parts of plants or to the locus thereof.
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